JP2017512892A - Secondary precipitation inhibitor in suspension polymerization reaction - Google Patents

Abstract

The use of a polymer as a secondary suspending agent in suspension polymerization is provided. The polymer comprises (i) the residue of at least one ester-containing monomer, wherein the ester-containing monomer (s) comprises one polymerizable carbon-carbon double bond per monomer and an ester group, and (ii) Monomer (s) containing sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group is one polymerizable carbon-carbon double bond per monomer, and sulfonate, sulfonic acid, sulfonate ester A sulfonamide or sulfonyl halide group containing sulfonate, sulfonic acid, sulfonic acid ester, a residue of at least one monomer containing a sulfonamide or sulfonyl halide group, the polymer being part of the ester group Is optionally partially hydrolyzed so as to form an alcohol group. - degree of hydrolysis is 0~30mol%.

Description

  The present invention relates to a suspending agent for suspension polymerization reaction. More specifically, the present invention relates to a secondary precipitation inhibitor for suspension polymerization reaction, although it does not exclude others. Further, the present invention uses a polymer as a secondary precipitation inhibitor for suspension polymerization, a suspension polymerization reaction composition, a method for carrying out a suspension polymerization reaction, and a secondary precipitation inhibitor for suspension polymerization. For polymers.

  In suspension polymerization reactions such as suspension polymerization of vinyl chloride, a primary precipitation preventing reagent and a secondary precipitation preventing reagent are often used. The primary suspending agent controls the coalescence of the polymer particles and thus mainly determines the particle size of the polymer so formed. Secondary suspending agents usually define secondary properties of the polymer particles, such as particle shape and porosity. Such secondary suspending agents usually contain partially hydrolyzed vinyl acetate (typical degree of hydrolysis is 35 to 55 mol%). The production of partially hydrolyzed polyvinyl acetate is a two-stage process with the production of polyvinyl acetate followed by partial hydrolysis. Therefore, it is desired to produce a secondary precipitation inhibitor that can function without hydrolysis.

  The present invention seeks to alleviate the above problems. Alternatively or additionally, the present invention seeks to provide an alternative and / or improved secondary precipitation inhibitor for suspension polymerization.

  According to a first aspect of the present invention, there is the use of a polymer as a secondary precipitation inhibitor in a suspension polymerization reaction, the polymer comprising (i) an ester-containing monomer (s) having one polymerizable per monomer. A residue of at least one ester-containing monomer comprising a carbon-carbon double bond and an ester group, and (ii) a monomer (s) comprising a sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group. At least one containing a sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group, including one polymerizable carbon-carbon double bond per sulfonate, and a sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group Contains one or more residues of two monomers The polymer is optionally partially hydrolyzed such that a portion of the ester group forms an alcohol group, the degree of hydrolysis of the polymer being 0-60 mol%, Provided.

  To avoid misunderstanding, the degree of hydrolysis is calculated from the residual acetate (RA) value. The residual acetate value of the polymer is measured by refluxing with an excess of 0.1N sodium hydroxide solution. A blank measurement without polymer is also performed. The remaining sodium hydroxide is titrated with 0.1N hydrochloric acid using a phenolphthalein indicator. The residual acetate ratio (% RA) in the polymer is calculated using the following formula.

  The degree of hydrolysis (DH) is calculated using the following equation:

  Applicants have surprisingly discovered that such polymers can function well as secondary suspending agents with low or no hydrolysis requirements. did.

  To avoid misunderstanding, the term “a part of the ester group” includes a state in which all ester groups are hydrolyzed.

  The method of the present invention optionally includes the use of an emulsion of the polymer as a secondary suspending agent. Alternatively, the polymer may be made by solution polymerization.

  The polymer may be made by emulsion polymerization and added to the suspension polymerization reaction mixture. The polymer may be added as an emulsion. To avoid misunderstanding, it should be noted here that the polymer can be added as an emulsion, but once added to the suspension polymerization reaction mixture, the emulsion may or may not retain its emulsion properties. Alternatively or additionally, the polymer may be made by emulsion polymerization. The polymer may be added to the suspension polymerization reaction mixture as a homogeneous solution in a solvent, for example, a mixture of water and methanol. Alternatively, or additionally, dry particles of polymer that can optionally be dispersed to form an emulsion may be added to the suspension polymerization reaction mixture. Optionally, dry particles of the polymer may be formed by making the polymer using emulsion polymerization and then drying the emulsion, thereby forming what is well known as a dry emulsion. Alternatively or additionally, the polymer may be dispersed as an emulsion in a solvent, optionally using, for example, a colloid.

  If the polymer is made by emulsion polymerization, the polymer optionally includes species. The species is usually located inside the polymer particle. Optionally, the polymer may be made by emulsion polymerization in the presence of seeds. The use of such species in emulsion polymerization is known to those skilled in the art. Such species are used to control particle size and particle size distribution. Such species are typically provided in an amount sufficient to cause substantially all polymer growth to occur at or around the species. The seed optionally includes a seed polymer. The seed polymer need not be the same as the polymer, that is, the seed polymer need not contain residues of the ester-containing monomers and sulfur-containing monomers described above. The seed should be colloidally stable in the emulsion used for emulsion polymerization. The seed may be synthesized in advance. Alternatively, the species may be synthesized in the system. For example, the species may be formed from one or both of at least one ester-containing monomer and at least one monomer containing a sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group.

  Thus, the present invention can provide the use of a polymer made by the above emulsion polymerization as a secondary precipitation inhibitor. The polymer made by emulsion polymerization may not be substantially hydrolyzed.

  Alternatively, the polymer may be made by polymerization in a dispersion medium, or solution polymerization or bulk polymerization.

  As mentioned above, the polymer may comprise a residue of one or more ester-containing monomers. For example, the polymer may comprise a vinyl acetate residue and a methyl methacrylate residue, or a vinyl acetate residue and a dimethyl maleate residue.

  The following description of ester-containing monomers can be applied to one or more monomers used to make a polymer.

  Optionally, the ester-containing monomer includes a polymerizable C═C group attached to the ester group, optionally via a linker. In general, it is preferred that there is no linking group between the polymerizable C═C group and the ester group. For example, an ester group can include, for example, an ester of an alkenoic acid. For example, the ester group may comprise an ester of acrylic acid, such as an ester of (meth) acrylic acid. The ester group can include, for example, an alkenyl alkanoate.

  The ester group may be located in the —O— moiety adjacent to the C═C group, as in the case of alkenyl alkanoates such as vinyl acetate, or in the case of alkyl acrylates such as methyl acrylate and methyl methacrylate. As such, a C═O moiety adjacent to the C═C group may be disposed.

The C═C group is optionally substituted at 1, 2 or 3 positions. For example, each substituent present is optionally halo, hydroxy, or optionally may be selected from one or more of the substituted C ₁ -C ₆ alkyl group.

  If the polymer is partially hydrolyzed so that at least some of the ester groups react to form an alcohol, at least 5% of the hydroxyl groups so formed, optionally at least 10%, optionally at least It is preferred that 20%, optionally at least 50%, optionally at least 70%, optionally at least 80%, optionally at least 90%, and optionally substantially all are directly bonded to the polymer. This can be accomplished using alkenyl alkanoate monomers in which the —O— moiety is directly attached to the C═C group.

  Ester-containing monomers are vinyl acetate, vinyl benzoate, vinyl 4-tert-butylbenzoate, vinyl chloroformate, vinyl cinnamate, vinyl decanoate, vinyl neononanoate, vinyl neodecanoate, vinyl pivalate, vinyl propionate , Vinyl stearate, vinyl trifluoroacetate, vinyl valerate, methyl vinyl acetate, propenyl acetate, methyl propenyl acetate, ethyl propenyl acetate, butenyl acetate, methyl butenyl acetate, vinyl propanoate, propenyl propanoate, vinyl butyrate Rate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl 2-propylheptanoate, vinyl nonanoate, vinyl neo Nanoeto, optionally containing one or more of the vinyl trifluoroacetate. For example, one or more of the above monomers can be the main monomer in that it provides more than 50 mol% of the content of ester-containing monomers. Alternatively or additionally, one or more of the above monomers can be a secondary monomer in that it provides less than 50 mol% of the content of the ester-containing monomer.

The ester-containing monomer optionally includes one or more esters of (meth) acrylic acid. This may be the case, for example, when the polymer is an emulsion polymer. In general, the preferred alkyl esters of (meth) acrylic _acid, C 1 _{-C 10} alkyl (meth) acrylates, preferably _C 1 _{-C 10} - may be selected from alkyl (meth) acrylate. Examples of such acrylate monomers include n-butyl acrylate, secondary butyl acrylate, ethyl acrylate, hexyl acrylate, tert-butyl acrylate, 2-ethyl-hexyl acrylate, isooctyl acrylate, 4-methyl-2-pentyl Examples include acrylate, 2-methylbutyl acrylate, methyl methacrylate, butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, and cetyl methacrylate. Other esters of (meth) acrylic acid include 4-acetoxyphenethyl (meth) acrylate, (meth) acryloyl chloride, 4- (meth) acryloylmorpholine, 2- (4-benzoyl-3-hydroxyphenoxy) ethyl ( (Meth) acrylate, [2-((meth) acryloyloxy) ethyl] trimethylammonium chloride, benzyl 2-propyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-{[( Butylamino) carbonyl] oxy} ethyl (meth) acrylate, tert-butyl 2-bromo (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, 2-carboxyethyl (meth) acrylate, 2-chloroethyl (meth) ) Acrylate, di (ethylene glycol) ethyl ether (meth) acrylate, di (ethylene glycol) 2-ethylhexyl ether (meth) acrylate, 2- (dimethylamino) ethyl (meth) acrylate, 3- (dimethylamino) propyl (meth) ) Acrylate, dipentaerythritol penta- / hexa- (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methyl acrylate, 2-ethyl (meth) acryloyl chloride, ethyl 2- (bromomethyl) (meth) acrylate, ethyl cis -(Β-cyano) (meth) acrylate, ethylene glycol dicyclopentenyl ether (meth) acrylate, ethylene glycol phenyl ether (meth) acrylate, ethyl 2-ethyl (meth) acrylate Ethyl 2-propyl (meth) acrylate, ethyl 2- (trimethylsilylmethyl) (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl ( (Meth) acrylate, hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isobutyl acrylate, isooctyl methacrylate, lauryl (meth) acrylate, methyl 2-acetamido (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 3- ( Trimethoxysilyl) propyl (meth) acrylate, 3,5,5-trimethylhexyl (meth) acrylate, 10-undecenyl (meth) acrylate, maleic acid, maleic anhydride, Methyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, di-2-ethylhexyl maleate (and the corresponding half ester of maleic acid), fumaric acid, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, Dibutyl fumarate, di-2-ethylhexyl fumarate (and the corresponding half ester of fumaric acid), methyl α-bromo (meth) acrylate, methyl 2- (bromomethyl) (meth) acrylate, pentabromobenzyl (meth) acrylate, penta Bromophenyl (meth) acrylate, pentafluorophenyl (meth) acrylate, poly (ethylene glycol) acrylate, methyl 2- (chloromethyl) (meth) acrylate, methyl 3-hydroxy-2-methylene butyrate, methyl Examples include 2- (trifluoromethyl) (meth) acrylate, octadecyl (meth) acrylate, and poly (ethylene glycol) methyl ether (meth) acrylate. For example, one or more of the above monomers can be the main monomer in that it provides more than 50 mol% of the ester-containing monomer content. Alternatively or additionally, one or more of the above monomers can be a secondary monomer in that it provides less than 50 mol% of the ester-containing monomer content.

  Residues of other monomers may be contained as comonomers, and examples of the other monomers include ethylene, 4-acetoxyphenethyl acrylate, 4-acryloylmorpholine, and 2- (4-benzoyl-3-hydroxyphenoxy) ethyl. Acrylate, [2- (acryloyloxy) ethyl] trimethylammonium chloride, benzyl 2-propyl acrylate, butyl acrylate, tert-butyl acrylate, 2-{[(butylamino) carbonyl] oxy} ethyl acrylate, tert-butyl 2-bromo Acrylate, 4-tert-butylcyclohexyl acrylate, 2-carboxyethyl acrylate, 2-chloroethyl acrylate, di (ethylene glycol) ethyl ether acrylate, di (ethyl) Glycol) 2-ethylhexyl ether acrylate, 2- (dimethylamino) ethyl acrylate, 3- (dimethylamino) propyl acrylate, dipentaerythritol penta- / hexa-acrylate, 2-ethoxyethyl acrylate, methyl acrylate, 2-ethylacryloyl Chloride, ethyl 2- (bromomethyl) acrylate, ethyl cis- (β-cyano) acrylate, ethylene glycol dicyclopentenyl ether acrylate, ethylene glycol phenyl ether acrylate, ethyl 2-ethyl acrylate, 2-ethylhexyl acrylate, ethyl 2-propyl acrylate , Ethyl 2- (trimethylsilylmethyl) acrylate, hexyl acrylate, 4-hydroxybutyl acrylate 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, hydroxypropyl acrylate, i-methyl acrylate, sobornyl acrylate, isobutyl acrylate, isooctyl acrylate, lauryl acrylate, methyl 2-acetamido acrylate, tetrahydrofurfuryl acrylate , 3- (trimethoxysilyl) propyl acrylate, 3,5,5-trimethylhexyl acrylate, 10-undecenyl acrylate, methyl methacrylate, maleic acid, maleic anhydride, dimethyl maleate, diethyl maleate, dipropyl maleate , Dibutyl maleate, di-2-ethylhexyl maleate (and corresponding half esters of maleic acid), fumaric acid, dimethyl fumarate Diethyl fumarate, dipropyl fumarate, dibutyl fumarate, di-2-ethylhexyl fumarate (and corresponding half ester of fumaric acid), methyl α-bromoacrylate, methyl 2- (bromomethyl) acrylate, pentabromobenzyl acrylate, penta Bromophenyl acrylate, pentafluorophenyl acrylate, poly (ethylene glycol) acrylate, methyl 2- (chloromethyl) acrylate, methyl 3-hydroxy-2-methylene butyrate, methyl 2- (trifluoromethyl) acrylate, and octadecyl acrylate, And poly (ethylene glycol) methyl ether (meth) acrylate.

  For the avoidance of doubt, it is noted here that the term “monomer” applies to oligomers and polymers containing polymerizable carbon-carbon double bonds. Such oligomers contain less than 5 repeat units, while the polymer contains 5 or more repeat units.

  As mentioned above, the polymer optionally comprises a residue of one or more monomers comprising sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide groups.

  The following description of monomers containing sulfonate, sulfonic acid, sulfonic acid ester, sulfonamide or sulfonyl halide groups can be applied to one or more such monomers used to make polymers.

Monomers containing a sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group typically contain a sulfonate (SO ₃ ⁻ ) group (optionally provided as a salt, eg, a sodium salt), a sulfonic acid (— SO ₃ H) group, sulfonic acid ester (—SO ₃ R, where R is any suitable group, eg, optionally substituted alkyl, aryl or alkenyl), sulfonamide (primary , Secondary or tertiary) or a sulfonyl halide (—SO ₃ X, where X is a halogen), including a polymerizable C═C group (optionally via a linker). In general, a linking group such as a C1-C6 alkylene group is optionally included (optionally substituted) between the polymerizable C═C group and the sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group. And optionally branched) alkylene linkers, such as methylene linking groups, etc. are preferably present.

  A linking group can comprise a chain of up to 10 atoms, optionally up to 8 atoms, and optionally up to 5 atoms. The linking group optionally includes one or more ethers and / or secondary or tertiary amino groups. The linking group is optionally substituted with one or more alkyl, halo or hydroxyl groups.

Examples of monomers containing sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide groups include sodium vinyl sulfonate, sodium (meth) allyl sulfonate, sodium allyl sulfonate, 2-methyl-2-propene-1 -Sodium sulfonic acid salt and 2-acrylamido-2-methylpropane sulfonic acid sodium salt, 3-sulfopropyl (meth) acrylate, sodium α-methylstyrene sulfonate, sodium ethylstyrene sulfonate, 1-allyloxy-2-hydroxypropyl Examples include sodium sulfonate. Likewise suitable are linear or branched C ₁ -C ₁₀ -alkylsulfonamides of acrylic acid or methacrylic acid. Also suitable are ω-alkene-1-sulfonic acids having 2 to 10 carbon atoms. Other examples include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 2-methacrylamido-2-methylpropane sulfonic acid, 2-acrylamidoethane sulfonic acid, 2-acryloyloxyethane sulfonic acid, 2-methacryloyloxy. Examples include ethanesulfonic acid, 3-acryloyloxypropanesulfonic acid, 2,2-ethylhexylaminoethanesulfonic acid, and 2-methacryloyloxypropanesulfonic acid, sodium 4-vinylbenzenesulfonate, and salts and esters thereof.

The C═C group is optionally substituted at 1, 2 or 3 positions. For example, each substituent present is optionally halo, hydroxy, or optionally may be selected from one or more of the substituted C ₁ -C ₆ alkyl group.

  Copolymers can contain up to 10 mol% of monomer residues containing sulfonate groups, sulfonic acid groups, sulfonate ester groups, sulfonamido groups or sulfonyl halide groups, based on the residual content of one or more ester-containing monomers. Up to 7 mol%, optionally up to 5 mol%, optionally up to 3 mol%, optionally up to 2 mol%, optionally up to 1 mol%, optionally at least 0.1 mol%, optionally at least 1 mol%, optionally At least 1.5 mol%, optionally 1-10 mol%, optionally 1-7 mol%, optionally 2-7 mol%, optionally 2-5 mol%, optionally 0.1-2 mol%, and optionally 0.1 It may contain 1.5 mol%.

  The copolymer optionally includes a residue of monomers that is not a residue of at least one ester-containing monomer or a residue of at least one monomer including sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide. For example, the copolymer optionally includes residues of vinyl monomers or vinyl aromatic monomers such as ethylene, styrene, alpha-methyl styrene, p-methyl styrene, t-butyl styrene or vinyl toluene. The copolymer can also include one or more of a solvent, a chain transfer agent, and an initiator.

  The copolymer optionally comprises at least 90% by weight (optionally the residue of at least one ester-containing monomer and at least one monomer comprising a sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group. At least 95% by weight, and optionally at least 98% by weight), and optionally a portion of the ester residue is hydrolyzed to provide a degree of hydrolysis of up to 60 mol%, the remainder of the polymer being at least one Residues of ester-containing monomers and other residues such as solvents, chain transfer agents and initiators that are not residues of at least one monomer including sulfonates, sulfonic acids, sulfonate esters, sulfonamides or sulfonyl halides It is a thing.

  The polymer may be one or more monomers represented by the following formula (1), in addition to or instead of the residue (s) of the at least one monomer comprising a sulfonate, sulfonic acid, sulfonate ester group, sulfonamide or sulfonyl halide group Of one or more residues.

Formula (1)
(Wherein at least one of A, B and C comprises at least one (and optionally only) polymerizable carbon-carbon double bond and of A, B and C At least one of -OH or a salt or ester thereof.

  To avoid misunderstanding, in formula (1), P is phosphorus and O is oxygen.

  Optionally, two of A, B and C comprise -OH or a salt or ester thereof, in which case two of A, B and C above may be the same or different.

  Optionally, two of A, B and C may comprise at least one (and optionally only) polymerizable carbon-carbon double bond, in which case one of A, B and C above The two can be the same or different.

  The ester of the —OH group can include, for example, an alkyl ester.

  The group (s) comprising at least one (and optionally only) polymerizable carbon-carbon double bond may comprise an acrylic acid group (or ester or salt thereof), an acrylamide group (or derivative thereof), or For example, it may contain vinyl or allyl groups.

  The monomer (s) comprising at least one phosphonic acid group (or salt or ester thereof) is optionally vinyl phosphonic acid (and methyl ester), 2-propene phosphonic acid (and diethyl ester), 2-hydroxyethyl phosphate (Meth) acrylate ester, 2- (methacryloyloxy) ethyl phosphate, α- (dialkylphosphonate) acrylate, β- (dialkylphosphonate) acrylate, dialkylphosphonate (meth) acrylate, N- (dialkylphosphonate) (meth) acrylamide, dimethyl (Methacryloyloxy) methyl phosphonate, dialkyl vinyl phosphonate (eg dimethyl vinyl phosphonate, diethyl vinyl phosphonate, diisopropyl vinyl phosphonate), allyl phos Phosphonic acid and allylphosphonic acid monoammonium salt, dimethyl-1-allyloxymethyl phosphonate, dialkyl vinyl ether phosphonate (such as 2-vinyloxyethyl phosphonate), diethyl 2-butenyl phosphonate, bis (2-methacryloxyethyl) phosphonate, Polyethylene glycol mono (meth) acrylate phosphate ester, polypropylene glycol mono (meth) acrylate phosphate ester, para-vinyl benzyl phosphonate, diethyl benzyl phosphonate, and salts and esters thereof.

  For example, the polymer may comprise a residue of one or more monomers of the formula (1) and contains at least one of the above containing a sulfonate group, a sulfonic acid group, a sulfonic acid ester group, a sulfonamide group or a sulfonyl halide group. One monomer residue may be substantially absent.

  In one embodiment, the copolymer is not hydrolyzed to any significant extent. In this case, the degree of hydrolysis is optionally 10 mol% or less, optionally 5 mol% or less, and optionally substantially zero. Applicants have surprisingly discovered that unhydrolyzed copolymers can function well as secondary stabilizers in suspension polymerization of vinyl compounds. This is especially true when the polymer is provided as an emulsion.

  When the copolymer is hydrolyzed, the degree of hydrolysis can optionally be less than 60 mol%, optionally 10-50 mol%, optionally 10-45 mol%, and optionally 10-40 mol%. The degree of hydrolysis can optionally be 10-30 mol%. Therefore, the degree of hydrolysis of the polymer can be 0-30 mol%.

  The polymer is optionally a substantially linear polymer.

  Alternatively, the polymer can be a branched polymer. Thus, the copolymer may comprise a residue of one or more polyunsaturated monomers, each containing a plurality of polymerizable unsaturated groups, such as C═C groups. The monomer can incorporate branching into the polymer.

  The at least one (optionally each) polyunsaturated monomer can include any monomer that can be polymerized by a free radical mechanism. The term “monomer” also encompasses oligomers (typically containing less than 5 repeat units) or polymers (typically containing 5 or more repeat units) with appropriate reactivity. .

  One or more (and optionally each) carbon-carbon double bond (if present) of at least one (and optionally each) polyunsaturated monomer is an ethylenic carbon-carbon double bond. possible.

  The at least one polyunsaturated monomer optionally includes at least two (and optionally at least three) polymerizable (optionally carbon-carbon) double bonds per molecule.

  The at least one polyunsaturated monomer can comprise a diunsaturated monomer, that is, it can comprise two and no more than two polymerizable (optionally C—C) double bonds. Examples of suitable diunsaturated monomers include di (meth) acrylates or diallyl compounds such as diacrylates and di (meth) acrylates such as ethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) Acrylates, and vinyl acrylates such as allyl (meth) acrylate, butadiene, diallyl succinate, diallyl carbonate, diallyl phthalate, and substituted analogs thereof. That.

  For example, the at least one polyunsaturated monomer can comprise a triunsaturated monomer, that is, can comprise 3 and up to 3 polymerizable (optionally C—C) double bonds.

  As trivalent unsaturated monomers, tripropylene glycol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,3,5-triallyl-1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trione ("TTT"), or diallyl maleate.

  The at least one polyunsaturated monomer may contain four (and only four) polymerizable (optionally C—C) double bonds. The tetravalent unsaturated monomer is, for example, pentaerythritol tetra (meth) acrylate.

  The at least one polyunsaturated monomer may comprise a pentavalent unsaturated monomer containing five (and only five) polymerizable (optionally C—C) double bonds. An example of a pentavalent unsaturated monomer is glucose penta (meth) acrylate.

  The polymer may optionally include a residue of one or more chain transfer agents. Such chain transfer agents can be used to control polymer weight. The one or more chain transfer agents can include thiol, alcohol or carbonyl-containing moieties. Thiols can include, for example, N-dodecyl mercaptan, tertiary dodecyl mercaptan, tert-nonyl mercaptan, pentaerythritol tetrakis (2-mercaptoacetate) or pentaerythritol tetrakis (3-mercaptopropionate). Chain transfer agents can include alcohols such as methanol, ethanol, isopropyl alcohol, butanol, etc., or chain transfer agents can be carbonyl-containing compounds such as acetaldehyde, propionaldehyde, butyraldehyde, pentanealdehyde, hexylaldehyde, benzylaldehyde, acetone. , Methyl ethyl ketone, and the like. Other suitable chain transfer agents are described in Kinetics and Mechanisms of Polymerization, Volume 1, Part 1, Chapters 1-12 and 4-2, Part C, 1967, Marcel Decker Inc. Can be found inside.

  The amount of chain transfer agent used in the process to produce the polymer will depend largely on the efficiency of the chain transfer agent. Efficient chain transfer agents (eg thiols) can usually be provided in much lower amounts than less efficient chain transfer agents (eg isopropyl alcohol).

  The polymer may optionally include a residue of one or more polymerization initiators. Such initiators can generate free radicals. As initiators, azo initiators such as azobis (isobutyronitrile) (AIBN), azobis (2-methylbutyronitrile), azbis (2,4-dimethylvaleronitrile), azobis (4-cyanovaleric acid), etc. Or oxidizing agents such as persulfates (eg potassium persulfate, sodium persulfate or ammonium persulfate), hydrogen peroxide, tertiary butyl hydrogen peroxide, oil-soluble peroxyesters such as dilauryl peroxide Or tert-butylperoxyneodecanoate, dibenzoyl peroxide, dicumyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxydiethyl acetate and tert-butylperoxybenzoate, Peroxy dicarbonate Such as di (n-propyl) peroxydicarbonate di (2-ethylhexyl) peroxydicarbonate or di (4-tert-butylcyclohexyl) peroxydicarbonate, or a redox couple such as dioxygen in combination with a reducing agent. Oxides such as hydrogen peroxide and sodium formaldehyde sulfoxylate or sodium dithionite or sodium metabisulphite or ascorbic acid (further examples of redox initiators are found in US 2007/0184732, in particular paragraph [0043] Or a combination of initiators. Examples of photoinitiator systems can be found in US 8603730, in particular rows 6 and 7 across the text. Optionally, the initiator may comprise a system capable of undergoing controlled radical polymerization, such as RAFT, ATRP or NMP.

The number average molecular weight M _n is optionally 300,000 or less, optionally 150,000 or less, optionally 50,000 or less, optionally 10,000 or less, optionally 5,000 or less. The number average molecular weight can be at least 1,000, and optionally at least 2,000. The number average molecular weight is optionally from 1,200 to 200,000, optionally from 1,400 to 150,000, and optionally from 1,500 to 120,000 g / mol.

The weight average molecular weight _Mw is optionally 2,000,000 or less, optionally 500,000 or less, optionally 100,000 or less, optionally 50,000 or less, and optionally 25,000 or less. The weight average molecular weight can be at least 5000, optionally at least 10,000, and optionally at least 15,000. The weight average molecular weight is optionally 5,000 to 50,000, optionally 5,000 to 40,000, optionally 8,000 to 40,000, and optionally 10,000 to 30,000 g / mol.

The above molecular weights _Mw and _Mn were measured by size exclusion chromatography (SEC) in THF solution (gel permeation chromatography, also known as GPC). Samples were PL-GPC-50 (registered) by an automated sampler using stabilized THF as the mobile phase and three consecutive PL gel® columns each having dimensions of 300 mm × 7.5 mm × 10 μm. Was injected into the trademark system. The system was calibrated using polystyrene standards, PS High Eastals provided by Agilent Technologies with an Mp molecular weight range of 6,035,000-580 g / mol. Samples for GPC analysis were prepared by drying 0.1 g of dry polymer in 20 mL of tetrahydrofuran (THF) after drying the solution or emulsion in a 20 ° C. drying box.

The K value was determined by measuring the solution viscosity of a dry polymer sample obtained by solution polymerization or emulsion polymerization. In this case, the K value measurement was equilibrated to 20 ± 0.2 ° C. in a water bath using a 2% (w / v) solution of the polymer in a suitable solvent (usually methanol or ethyl acetate). Performed in a “C” U-tube viscometer. The relative solution viscosity η _r was calculated using the time for the equilibrated solution to flow between the two marks in the capillary.

  Thereafter, the K value was derived from the following equation.

  In the formula, c = polymer concentration (expressed in g / 100 mL solution). A dry sample of the polymer was prepared by drying a sample of a solution or emulsion (optionally solubilized with methanol) under a stream of air at 20 ° C.

  The K value (Kv) of the polymer is optionally 20-90, optionally 25-85, optionally 30-80, optionally 30-40, and optionally 70-80.

  The polymer can include one or more setting inhibitors. The one or more set inhibitors may include one or more of one or more surfactants and one or more water soluble polymers (often known to those skilled in the art as “colloids”). Setting inhibitors inhibit the setting of polymer particles and stabilize the emulsion.

  Optionally, the surfactant can be anionic, nonionic or cationic.

  Surfactant is 0-20 wt% by weight based on the total weight of monomers (ie, ester-containing monomer (s) and monomer (s) containing sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide groups). , Preferably in an amount of 0-10 wt%, more preferably in an amount of 0-5 wt%. The amount of surfactant optionally occupies 0.1 wt% or more, optionally 0.5 wt% or more, and optionally 1 wt% or more based on the total weight of monomers as defined above. The amount of surfactant is optionally up to 2 wt%, optionally up to 3 wt%, optionally up to 5 wt%, optionally up to 10 wt% based on the total weight of the monomers. The polymer may be synthesized without a surfactant.

  One or more colloids can be used instead of or in addition to one or more surfactants. Suitable colloids include polyhydroxy compounds such as partially acetylated polyvinyl alcohol, casein, hydroxyethyl starch, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyethylene glycol, and gum arabic. The one or more colloids can include polyvinyl alcohol. In general, these protective colloids are used in a content of 0 to 10 wt%, optionally 0 to 5 wt%, based on the total weight of the monomers defined above. The amount of protective colloid optionally comprises 0.1 wt% or more, optionally 0.5 wt% or more, and optionally 1 wt% or more based on the total weight of the monomers as defined above. The amount of surfactant is optionally up to 2 wt%, optionally up to 3 wt%, optionally up to 5 wt%, optionally up to 10 wt%, and optionally up to 20 wt% based on the total weight of the monomers. Occupy. The polymer may be synthesized without colloid.

  It has been found that the above polymers can be successfully used as secondary suspending agents in suspension polymerization reactions even if not hydrolyzed. By omitting the hydrolysis step, less vinyl acetate is required per ton of final product produced. That is, it is a much more atomic efficient process than conventional processes for producing partially hydrolyzed polyvinyl acetate secondary precipitation inhibitors by hydrolysis processes.

  The polymer may be present in the form of an emulsion. The polymer particle size is optionally 40-1000 nm, optionally 100-800 nm, and optionally 200-600 nm.

  The particle size may be measured using any suitable technique, but is usually measured using the strength average particle size of the emulsion particles, which is from Malvern Instruments, Inc. using Zetasizer 6.2®. It was measured by dynamic light scattering (DLS) at a temperature of 25 ° C. using a Zetasizer Nano-S®. The instrument was calibrated using standard polystyrene latex provided by Malvern Instruments, which exhibits a particle size of 220 ± 6 nm in water. Samples were diluted with deionized water.

  When the emulsion is first made, it optionally has a total solids content of at least 5%, optionally at least 15%, optionally at least 35%, optionally up to 70%, optionally up to 65%, and optionally up to 60%. Have. The emulsion is optionally diluted before being added to the suspension polymerization reagent.

  When the emulsion is made, it may optionally be concentrated by removal of volatile components. The emulsion may optionally be separated from the water by any known process known in the state of the art, such as spray drying or filtration followed by coagulation with salt. The dry polymer may optionally be provided with a fluidizing agent such as calcium carbonate or silica to prevent “blocking” of the dry powder.

  Optionally, the emulsion may be added directly to the polymerization reactor in its originally formed form, or it may be diluted with process water prior to addition, or by any aqueous reagent that flows into the reactor, for example primary precipitation. You may dilute with an inhibitor solution. Optionally, the dry emulsion may be added directly to the reactor as a solid material, and optionally the dry emulsion powder may be added to one of the process streams, eg, the primary suspending agent solution, or the dry emulsion powder May be reconstituted as an emulsion and optionally added to the reactor by incorporation into the primary suspending agent solution.

  The pH of the emulsion when initially made can optionally be 9 or less, optionally 7.5 or less, optionally 6.5 or less, optionally 4-6, optionally 1-2. Thus, the pH of the diluted emulsion (added to the suspension polymerization reagent) will depend on the dilution of the emulsion. The emulsion optionally includes one or more buffering agents. The buffer keeps the pH in the desired range (eg 4-6), which can prevent the pH from dropping to a level where undesirable hydrolysis of the polymer occurs.

  The viscosity of the emulsion is less than 50 Ps, optionally less than 30 Ps, typically less than 5 Ps, typically less than 1 Ps. Viscosity is measured using a Brookfield DV-I ™ viscometer, spindle 1 at 20 ° C. and 20 rpm.

  The suspension polymerization reaction is well known to those skilled in the art and is as defined by IUPAC. Suspension polymerization is a polymerization that forms a polymer in monomer droplets or monomer-solvent droplets in a continuous phase that is a non-solvent for both the monomer and the polymer formed. Furthermore, the droplets have an average particle size greater than 1 micron, typically greater than 5 microns, and optionally greater than 10 microns. This definition can be found in Pure Appl Chem, Volume 83, No. 12, pp. 2229-2259, September 2011, “Terminology of polymers and dispersed phases (IUPAC recommendation 2011)”. Similarly, those skilled in the art will understand the term “secondary precipitation inhibitor”. To avoid misunderstanding, secondary suspending agents are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A21, pages 717-742, 1992, VCH Publishers Inc, especially pages 721-723. ing. For the avoidance of doubt, the above references refer to “secondary protective colloids” instead of “secondary precipitation inhibitors”. The teachings on “secondary protective colloids” in the above references are incorporated herein by reference. Secondary precipitation inhibitors are also known as secondary stabilizers.

  According to a second aspect of the present invention, there is provided a secondary suspending agent composition for suspension polymerization of vinyl compounds, wherein the composition comprises (i) one ester-containing monomer (s) per monomer. Residue of at least one ester-containing monomer containing a polymerizable carbon-carbon double bond and an ester group, and (ii) containing a sulfonate group, sulfonic acid group, sulfonic acid ester group, sulfonamide group or sulfonyl halide group Sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl, wherein the monomer (s) contain one polymerizable carbon-carbon double bond per monomer and a sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl chloride group Containing one or more residues of at least one monomer containing a halide group. Including a solution or emulsion of the copolymer, the polymer is optionally partially hydrolyzed such that some of the ester groups form alcohol groups, and the degree of hydrolysis of the polymer is 0-60 mol%. Certain secondary suspending agent compositions for suspension polymerization of vinyl compounds are provided.

  The polymer used in the secondary suspending agent composition of the second aspect of the invention may comprise the features described above with respect to the use of the polymer of the first aspect of the invention. Similarly, the emulsion used may include the features described above with respect to the first aspect of the invention. For example, the polymer may be made by emulsion polymerization. If the polymer is made by emulsion polymerization, the polymer can include seeds.

According to a third aspect of the present invention, a suspension polymerization reaction composition comprising:
A continuous phase in which droplets of one or more monomers to be polymerized are dispersed;
One or more primary suspending agents, and (i) a residue of at least one ester-containing monomer, wherein the ester-containing monomer (s) comprise one polymerizable carbon-carbon double bond per monomer, and an ester group, and (Ii) one polymerizable carbon-carbon double bond per monomer containing sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group, and sulfonate, sulfonic acid, sulfonate ester, sulfonamide Or at least one 2 comprising a copolymer (optionally an emulsion of the copolymer) of one or more residues of at least one monomer comprising a sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group comprising a sulfonyl halide group. Subsequent precipitation inhibitor The polymer is optionally partially hydrolyzed so that a part of the ester group forms an alcohol group, and the degree of hydrolysis of the polymer is 0 to 60 mol%. A composition is provided.

  The copolymer may have the characteristics described above with respect to the use of the polymer according to the first aspect of the invention. For example, the polymer can be made by emulsion polymerization.

  The one or more monomers to be polymerized may include monomers that contain polymerizable vinyl (C = C) groups, and optionally one or more comonomers. For example, monomers include vinyl halide (such as vinyl chloride and vinylidene chloride), alkenyl alkanoate (such as vinyl acetate), alkyl acrylate (such as ethyl acrylate, butyl acrylate or 2-ethylenehexyl acrylate), alkyl methacrylate (such as methyl methacrylate), Or it may contain one or more of acrylonitrile. The copolymer, if present, is usually provided in an amount less than the “major” monomer. The copolymer may have monomeric units distributed statistically or in bulk along the polymer chain. Preferably, the poly (vinyl chloride) is selected from poly (vinyl chloride) homopolymers and copolymers with vinyl acetate, acrylonitrile and / or alkyl (meth) acrylates such as vinyl chloride / vinyl acetate copolymers. For example, in the production of PVC, vinyl chloride is provided in greater amounts than the copolymer, which can include, for example, vinyl acetate and vinyl alcohol.

  The primary suspending agent may optionally include one or more polyvinyl acetates, typically having a degree of hydrolysis of about 70-90 mol% (thus the suspending agent is polyvinyl acetate-co-polyvinyl alcohol). Some), also known as partially hydrolyzed polyvinyl acetate or polyvinyl alcohol. The primary suspending agent may contain more than one component. Optionally, the primary suspending agent may comprise a cellulosic polymer such as hydroxypropylmethylcellulose or hydroxyethylcellulose. Specific examples of primary suspending agents are described in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, 1992, p. 722, Table 3, the teachings of which are incorporated herein by reference. The primary suspending agent can include one or more cellulosic polymers. The primary suspending agent can include one or more polyvinyl alcohols and one or more cellulosic polymers. The amount of one or more polyvinyl alcohols is usually greater than the amount of one or more cellulosic polymers.

  The monomer to be polymerized can be polymerized using radical addition polymerization, and thus the reaction composition can be suitable for radical addition polymerization. The polymerization process may be an addition polymerization process. The polymerization process may be a controlled living radical process.

  The composition optionally includes one or more initiators and one or more additional secondary suspending agents. Usually, the continuous phase is aqueous.

  The composition comprises 100 parts by weight of one or more monomers to be polymerized, 85-130 parts by weight (eg 90-130 parts by weight) of continuous phase (eg water), 0.04-0.22 parts by weight of primary suspending agent. Parts (for example, 0.05 to 0.15 parts by weight), the secondary precipitation inhibitor 0.001 to 0.20 parts by weight including the polymer, and 0.03 to 0.15 parts by weight of initiator (for example, 0.03 to 0.12 parts by weight or 0.03 to 0.10 parts by weight).

In order to improve the morphology of the resulting poly (vinyl chloride) granules, further additives such as:
One or more additional secondary suspending agents, one or more tertiary suspending agents, one or more buffers, oxygen, one or more chain transfer agents or chain extenders, and one or more chain terminators, one or more oxidations. An inhibitor, one or more of one or more accumulation inhibitors, and the like can be added. Although the primary function of the primary protective colloid is to control particle size, the primary protective colloid also affects porosity and other morphological characteristics. In addition, an additional amount of primary suspending agent or another polyvinyl alcohol can be added during the polymerization to improve bulk density and optionally control foaming to prevent undesirable thermal history in the resin. Also good.

  A variety of free radical initiators that are soluble in the monomer (s) can be used, including diacetyl peroxides, peroxydicarbonates and alkylperoxyesters, and azo initiators and benzoyl peroxides. Mixtures of various initiators can also be used. Specific examples of initiators are listed in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, 1992, p. 723, Table 4, the teachings of which are incorporated herein by reference.

  The composition optionally comprises a primary suspending agent in a greater weight than the secondary suspending agent. The composition optionally includes a secondary suspending agent in a greater weight than the primary suspending agent.

  The weight of the primary suspending agent used in the composition is optionally at least 0.5 times, optionally at least 1.0 times, optionally at least 1.2 times, optionally the weight of the secondary suspending agent used. At least 1.5 times, optionally at least 1.8 times, optionally at least 2.0 times, optionally at least 5.0 times, optionally at least 10 times, optionally at least 20 times, optionally at least 30 times, optionally At least 50 times, and optionally at least 90 times.

  The composition is optionally 20-2000 ppm, optionally 50-1000 ppm, optionally 100-800 ppm, optionally 100-600 ppm, and optionally the secondary precipitation inhibitor, based on the weight of the one or more monomers to be polymerized. Optionally 200-500 ppm included. The calculated ppm amount is based on the solids content of the polymer.

  The composition optionally includes one or more initiators. A variety of free radical initiators that are soluble in the monomer (s) can be used in suspension and bulk polymerizations, including diacetyl peroxide, peroxydicarbonate and alkyl peroxyesters, as well as azo initiators and benzoyl peroxide. Includes oxides. Mixtures of various initiators can also be used. Specific examples of initiators are listed in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, 1992, p. 723, Table 4, the teachings of which are incorporated herein by reference.

  As mentioned above, the one or more monomers to be polymerized optionally include vinyl chloride and optionally a copolymer. Within the scope of the present invention, the term “poly (vinyl chloride)” includes not only a homopolymer of vinyl chloride but also one or more comonomers (based on the total weight of the monomers) up to 60% by weight, typically Also included are copolymers of vinyl chloride having up to 30% by weight, preferably up to 20% by weight, more preferably up to 17% by weight. Usually, comonomer is vinylidene chloride, vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Hydroxyl alkyl acrylate, (meth) acrylic acid, (meth) acrylonitrile, vinyl isobutyl ether, vinyl fluoride, vinylidene fluoride, maleic anhydride and esters thereof, ethylene, propylene, styrene, and butadiene, and mixtures thereof Is done. The copolymer may have monomeric units distributed statistically or in bulk along the polymer chain. Preferably, the poly (vinyl chloride) is a poly (vinyl chloride) homopolymer and a copolymer with vinyl acetate, acrylonitrile and / or alkyl (meth) acrylate, such as 83 to 93 wt% polymerized vinyl chloride units and 17 A vinyl chloride / vinyl acetate copolymer typically comprising ˜7 wt% polymerized vinyl acetate units; typically 40-75 wt% polymerized vinyl chloride units and 25-60 wt% polymerized acrylonitrile units A vinyl chloride / acrylonitrile copolymer comprising; and a vinyl chloride / alkyl (meth) acrylate copolymer typically comprising 98-75% by weight polymerized vinyl chloride units and 2-25% by weight polymerized alkyl (meth) acrylate units. Rimmer is selected from such. Most preferably, the poly (vinyl chloride) is a poly (vinyl chloride) homopolymer.

According to a fourth aspect of the present invention, there is provided a method for producing a polymer using suspension polymerization, the method comprising:
(I) a residue of at least one ester-containing monomer, wherein the ester-containing monomer (s) comprise one polymerizable carbon-carbon double bond per monomer and an ester group, and (ii) sulfonates, sulfonic acids, sulfonic acids Sulfonate, sulfone, wherein the monomer (s) containing an ester, sulfonamide or sulfonyl halide group contains one polymerizable carbon-carbon double bond per monomer, and a sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide group One or more monomers in the presence of a secondary suspending agent comprising a copolymer (and optionally an emulsion of the copolymer) comprising one or more residues of at least one monomer comprising an acid, sulfonate ester, sulfonamide or sulfonyl halide group Polymerize The polymer is optionally partially hydrolyzed so that some of the ester groups form alcohol groups, and the degree of hydrolysis of the polymer is 0 to 60 mol% or less, suspended A method of producing a polymer using polymerization is provided.

  The method can include polymerizing one or more monomers in the presence of one or more primary suspending agents.

  The method can include polymerizing one or more monomers in the presence of one or more initiators.

The method comprises one or more monomers:
One or more additional secondary suspending agents, one or more tertiary suspending agents, one or more buffers, oxygen, one or more chain transfer agents or chain extenders, and one or more chain terminators, one or more oxidations. Polymerization in the presence of one or more of an inhibitor and one or more accumulation inhibitors may be included.

  The secondary suspending agent (s) may have the properties and characteristics described above with respect to the use of the first aspect of the invention and the composition of the second and third aspects of the invention.

  The method supplies a reactor with an initial charge comprising a liquid forming a continuous phase (typically water), optionally a secondary suspending agent as described above, and optionally one or more primary suspending agents. Optionally including. Thereafter, one or more monomers to be polymerized are added to the initial charge.

  Optionally, at least some of the primary suspending agent, and optionally at least some of the secondary suspending agent, are combined with one or more monomers to be polymerized, optionally in part or all of the liquid that forms a continuous phase. It may be added into the preheated reactor. Optionally, the reactor is then charged with one or more initiators. In general, the reactor inner wall may be coated with an accumulation inhibitor to prevent poly (vinyl chloride) adhesion to the walls, stirrer, cooling cage (if present) and baffle (if present). Good. Optionally, at least some initiator may be added along with water and one or more primary suspending agents, or may be added after the introduction of one or more monomers to be polymerized. After or during the charge, the reactor contents are usually heated to a temperature of 40-75 ° C. which can result in some initiator decomposition.

  In certain cases, the reaction is a strong exothermic reaction, in which case adding additional continuous phase liquid (optionally with additional primary and / or secondary suspending agents) or, for example, a jacket, The temperature may be controlled by removing heat by using an internal coil or cooler. Stirring is usually continued throughout the reaction. The reaction is usually stopped at a conversion of 80-95%, for example 80-90%, usually at a given pressure, generally by using a chain terminator and / or discharging unreacted monomers.

  The method of the fourth aspect of the invention may comprise forming a reaction composition according to the third aspect of the invention.

  According to a fifth aspect of the present invention there is provided a polymer (optionally made by emulsion polymerization) as defined for use as a secondary precipitation inhibitor in the first aspect of the present invention. The polymer may have the characteristics described above for use in the first aspect of the invention.

  It will be appreciated that features described with respect to one aspect of the invention may be incorporated into other aspects of the invention. For example, the method of the fourth aspect of the invention may incorporate any feature described with respect to the use of the first aspect of the invention, and vice versa.

  The invention will now be described by way of example only with reference to FIG. 1, firstly described with respect to a polymer made by solution polymerization (in part 1) and then by emulsion polymerization (in part 2). The polymer produced will be described.

FIG. 1 shows how vinyl chloride monomer (VCM) (%) changes over time to a polyvinyl chloride polymer made using the polyvinyl acetate / polyvinyl alcohol example according to an embodiment of the present invention. Show.

Part 1-Polymers made by solution polymerization Copolymer of A-vinyl acetate and sodium 2-methyl-2-propene-1-sulfonate
Table 1. A-Material

  A copolymer of vinyl acetate (“VAc”) and the sulfonate monomer 2-methyl-2-propene-1-sulfonic acid sodium salt (“NaMPSA”) was synthesized using the method shown in Table 1.1. MeOH is methanol, IPA is isopropyl alcohol, and TBPEH is t-butylperoxy-2-ethylhexanoate, an organic peroxide initiator.

  Briefly, in the initial stage, NaMPSA, methanol, isopropyl alcohol and vinyl acetate were charged into the reactor (1 liter volume reactor), the contents were agitated and a nitrogen stream was installed. The reagent was heated to reflux (85 ° C.). The initiator was added after 30 minutes of reflux. After an additional 30 minutes of refluxing, the addition of the composition labeled “addition 1” (including vinyl acetate, initiator, methanol and isopropyl alcohol) and additional NaMPSA was started (individually). The addition process took 210 minutes. As shown in Table 1.1, 30 minutes after the addition of NaMPSA and the composition labeled “Addition 1”, additional initiator was added and reflux continued for an additional 120 minutes.

Table 1.1-General methods used to make polymers used as secondary suspending agents

  The above method was performed while changing the amount of NaMPSA, adjusting the isopropanol concentration in order to keep the molecular weight substantially constant, and monitoring the conversion rate. The results are shown in Table 1.2.

Table 1.2-Polymer properties as a function of sulfonate content

  The K value was determined by the single point viscometry method using a calibrated U-shaped viscometer using a 2% (w / v) ethyl acetate solution of the polymer in the method described above.

  Solution viscosity = (recorded 2% (w / v) solution flow time) / (recorded ethyl acetate flow time)

  The influence on the properties of the polymer in scale-up was investigated. The results are shown in Table 1.3. Using a 4 liter reactor, 4 times the amount of reagents was used to essentially reproduce the method shown in Table 1.1 used to obtain the polymer.

Table 1.3-Polymer properties as a function of sulfonate content in a 4 liter reactor

  The conversion levels of the polymers prepared on the 1 liter and 4 liter scales were comparable. Scale-up seemed to increase the K value.

The actual amount of NaMPSA incorporated into the polymer was measured by measuring residual NaMPSA by HPLC using the following method.
Column: Ascentis Express® C8 15 cm * 4.6 mm, 2.7 μm (provided by Sigma Supelco)
Mobile phase: Acrylonitrile: Demineralized water 50:50 + 1 ml / liter of acetic acid Wavelength: 190 nm
Flow rate: 0.8 ml / min Column temperature: 40 ° C
Outflow time: 10 minutes

  A 1000 ppm NaMPSA standard was prepared by weighing 0.1 g NaMPSA into a 100 ml volumetric flask and allowing the acrylonitrile: demineralized water to reach the standard using a 50:50 solution. Standards of 100, 50, 10 and 5 ppm NaMPSA were prepared from this stock solution by appropriate dilution. These standards transferred to HPLC vials were run under the conditions described above.

  Samples were prepared by weighing 0.1 g sample into a 10 ml volumetric flask and reaching the standard using a 50:50 solution of acrylonitrile: demineralized water. When the samples were dissolved, they were treated with a Carrez® Clarification Reagent Kit (BioVision Inc.) and the resulting precipitate was centrifuged. The supernatant was gently transferred into an HPLC vial and run under the above conditions.

  Thereafter, as shown in Table 1.4, the incorporation rate (%) of NaMPSA into the polymer could be determined based on the measured value and the theoretical value of NaMPSA. In Table 1.4 below, C.I. Ex. 1 is Comparative Example 1.

Table 1.4—Measurement of polymer to theoretical NaMPSA content NaMPSA content

Using GPC, the molecular weight (number average molecular weight, M _n ; weight average molecular weight, M _w ) of the polymer was determined as shown in Table 1.5.

Table 1.5-Molecular weight of copolymers used as secondary suspending agents

  In the table, C.I. Ex. 2 is Alcotex (R) A522P, a standard secondary suspending agent with low hydrolysis provided by Synthomer (UK).

M _w and M _n were measured by size exclusion chromatography (SEC) in THF solution (gel permeation chromatography, also known as GPC). Samples were PL-GPC-50 (registered) by an automatic sampler using stabilized THF as the mobile phase and three consecutive PL gel columns each having dimensions of 300 mm × 7.5 mm × 10 μm. Into the trademark). The system was calibrated using polystyrene standards provided by Agilent Technologies with an Mp molecular weight range of 6,035,000-580 g / mol.

Note that the higher the level of sulfonation, the smaller M _w and M _n . Furthermore, the polydispersity (PDI) (M _w / M _n ) was relatively high. Polymer testing indicated that the oligomer level has a defined limit for the product to be considered a polymer.

  A secondary emulsion of the polymer of Example 1.8 was made. Using a Dispermill Yellow-Line 2075® high shear disperser (Atpen Engineering NL.), Alcotex® 88-47 (88 mol% hydrolyzed polyvinyl alcohol available from Synthomer, UK) Phase inversion was observed while stirring at 6500-7500 rpm in a solution of the polymer of Example 1.8 (50% (w / w) ethyl acetate solution) in which a 2% (w / w) aqueous solution was dissolved in ethyl acetate. Added dropwise until The sample thus obtained was then stripped under vacuum to remove residual ethyl acetate.

1. B. Production of PVC using non-hydrolyzed copolymer obtained by solution polymerization The polymer made according to the above method was used as a secondary precipitation inhibitor in the production of PVC.

The polymerization was carried out in a 1 liter stainless steel reactor under the following conditions.
Table 1.6-1 General conditions for manufacturing PVC on 1 liter scale

  Demineralized water, suspending agent, buffer and initiator are all 1 liter Buchi® stainless steel reaction (pre-coated with Alcotex® 225 accumulation inhibitor provided by Synthomer, UK) The container was filled and assembled on the tool. Strategies were planned to give the final particle size unchanged from typical commercial products. The reactor was then pressure tested and degassed to atmosphere, after which the vinyl chloride monomer was charged with a volume atomizer under nitrogen pressure. A suspension of vinyl chloride was prepared under stirring at about 750 rpm. The reactor is then heated to the desired polymerization temperature of 57 ° C. within 6 minutes under stirring at 750 rpm, stirring is continued at about 750 rpm, the maximum pressure is recorded, and a pressure drop of 0.2 MPa Later the reaction was stopped (by cooling and degassing to atmospheric pressure). The reactor was then evacuated to about 50 kPa for 45 minutes. The reactor contents were then gently transferred to a filter funnel and washed twice with 1% (w / w) sodium lauryl sulfate solution (as an antistatic treatment). Thereafter, the sample was placed in a convection fan oven at 50 ° C. for 12 hours and dried.

The resulting PVC samples were analyzed for particle size (D ₅₀ ), particle size distribution (GSD), low temperature plasticizer absorbency (CPA), bulk density (BD) and fill factor (PF). The measurement of these parameters is described below.

D ₅₀ -This is a measure of particle size (typically given in microns) and is thus determined. 12.5 g of resin is weighed and placed on a stack of 315, 250, 200, 160, 100 and 75 micron sieves, respectively, and a collection pan to collect what passes through the 75 micron sieve . The stack is fixed on a vibrator and shaken for 15 minutes. Record the mass of resin in each sieve and divide each value by 12.5 to get a measure of the percentage of total mass captured by that sieve. The value is plotted on a logarithmic graph and the value reaching 50% of its mass is determined.

GSD-particle size distribution. GSD by determining the particle size reaches 84% of the amount of grain size and a resin mass to reach 16% of the mass of resin with the resulting graph for D ₅₀ particle size measurement is determined The Then, taking the difference between the particle size reaches 84% of the particle size and mass to reach 16% of the mass, by dividing the result by D _50, GSD is calculated.

BD—Bulk Density—A quantity of resin is placed in a fluid bed dryer and dried at 50 ° C. for 1 hour. The resin is cooled for 1 hour. Thereafter, in accordance with ASTM 1895B, the resin is poured through a funnel strictly into a 100 cm ³ stainless steel container and the container is weighed. Level the accumulated resin with a sharp blade and weigh the container. The BD (bulk density) can be calculated from the mass and volume of the resin in the container.

  CPA-CPA (low temperature plasticizer absorbency) can be determined by carefully weighing 2.5 g of resin and 4 g of dioctyl phthalate (plasticizer) into a container with a membrane. Jacket the vessel (to give the same value as the ASTM standard) and centrifuge at 3000 rpm for 1 hour. Again, the container is weighed to determine the mass of plasticizer adsorbed on the resin. A percentage of the resin mass can be calculated.

The PF-filling ratio is a measure of how well the resin grains are packed. It is calculated this way.

  The properties of PVC polymers obtained using non-hydrolyzed polyvinyl acetate are characterized by Alcotex®, a commercially available conventional partially hydrolyzed polyvinyl acetate secondary precipitation inhibitor available from Synthomer (UK). Table 1.7 along with a number of implementations based on 552P (also known as C.Ex.2). The non-hydrolyzed product was added to the PVC reactor in the form of a methanol solution. The polymers shown in Table 1.7 were used as secondary precipitation inhibitors in the production of PVC.

Table 1.7-1 Properties of PVC as a function of secondary suspending agent produced in a 1 liter reactor

N / D—indicates that the property was not measured because the particle size D ₅₀ was greater than 250 microns.

  Unmodified polyvinyl acetate (C. Ex. 1) was used as a control for this series of experiments. Addition of the sulfonated comonomer increased the porosity and decreased the particle size of the PVC resin. However, the tendency for particle size to increase with increasing amount of sulfonated comonomer is apparent.

  Examples of non-hydrolytic sulfonation when sufficient particle size values are obtained and C.I. Ex. Comparing the results of 2 indicated that comparable CPA values were observed, which was unexpected. The CPA value reflects the achievable porosity within the PVC grain, and therefore reflects the ease with which the resin can be plasticized in use, or the ease with which the VCM can be stripped from the resin at the end of polymerization. . A scale-up experiment in a 10 liter reactor was conducted using several polymers identified as potentially useful as secondary suspending agents in a 1 liter experiment. The following conditions were used on this scale.

Table 1.8-General method for manufacturing PVC on 10 liter scale

  Following the pressure test, all of the demineralized water, suspending agent and buffer are to a 10 liter stainless steel reactor (pre-coated with Alcotex® 225 accumulation inhibitor provided by Synthomer, UK). Filled. Strategies were planned to give the final particle size unchanged from typical commercial products. Thereafter, the vinyl chloride monomer was charged with a flow meter under nitrogen pressure. A suspension of vinyl chloride was prepared under stirring at 600 rpm. The reactor was then heated to 57 ° C. while continuing to stir at 600 rpm. When the batch contents reached 57 ° C., the initiator was charged into the container under nitrogen pressure. The reactor pressure at the time of initiator addition was recorded and the reaction was stopped (by addition of stop agent, cooling and degassing to atmospheric pressure) after a pressure drop of 0.2 MPa. The reactor was then evacuated to about 80 kPa for 45 minutes. The reactor contents were then gently transferred to a filter funnel and washed twice with 1% (w / w) sodium lauryl sulfate solution (as an antistatic treatment).

  The results of these experiments are shown in Table 1.9.

Table 1.9 Properties of PVC as a function of secondary suspending agent produced in a 10-liter reactor

  Comparing the CPA results of the sulfonated polymers against conventional secondary suspending agents indicated that they were similar or slightly lower, but the bulk density values were comparable. Is or has become higher.

1. Partially Hydrolyzed Copolymer of C-Vinyl Acetate and NaMPSA A number of the above polymers were hydrolyzed using either acid or base catalysts. The hydrolysis of polyvinyl acetate is well known to those skilled in the art. Further guidance on hydrolysis can be found in C.I. A. “Polyvinyl alcohol developments” edited by Finch, (C) 1992 John Wiley & Sons, Chapter 3: F. L. Marten, C.I. W. Zvanut, Hydrology of Polyvinyl Acetate to Polyvinyl Alcohol, pages 57-77. The resulting hydrolysis values are shown in Table 1.10 as a function of catalyst, starting polymer and hydrolysis time.

Table 1.10-Partially hydrolyzed polymers for use as secondary precipitation inhibitors

1. D-Production of PVC using hydrolyzed copolymers obtained by solution polymerization A number of examples identified in Table 1.10 were tested as potential secondary precipitation inhibitors in the polymerization of vinyl chloride on a 1 liter scale. . The properties of the PVC so produced are shown in Table 1.11. The general method described above for producing PVC in a 1 liter reactor was used. The hydrolyzed example polymer was added as a methanol solution.

Table 1.11-Properties of PVC made with partially hydrolyzed polymers

N / D—indicates that the property was not measured because the particle size D ₅₀ was greater than 250 microns.

  The CPA value obtained from the sulfonated polymer is C.I. Ex. It was similar to that of the two controls, and tended to decrease with a decrease in the degree of hydrolysis.

  The particle size values obtained from the sulfonated polymer showed a dependence on the degree of hydrolysis of the sample and increased gradually with increasing hydrolysis and increasing sulfonation.

  The filling rate and bulk density of PVC made with partially hydrolyzed polymers are standard C.I. Ex. At least as much as those of PVC made with two polymers.

Part 2-Polymers made by emulsion polymerization A—A copolymer of vinyl acetate and 2-methyl-2-propene-1-sulfonic acid sodium salt made by emulsion polymerization.

Table 2. A-Material

  The synthesis of an emulsion copolymer of vinyl acetate (“VAc”) and sulfonate 2-methyl-2-propene-1-sulfonic acid sodium salt (“NaMPSA”) will now be described.

250 g of water (H ₂ O) and the required amount of NaMPSA were charged into a 1 liter reactor and heated to 70 ° C. with stirring. When the temperature reached 70 ° C., 10 g of NaPS aqueous solution (13.8 wt%) was introduced. After 5 minutes, a monomer (150 g of VAc mixed with 50 g of IPA) and 40 g of an aqueous NaPS solution (13.8 wt%) were separately fed over 1 hour. When these additions were complete, a solution of ₂ g NaMPSA in 50 g H ₂ O was added to the reactor and the reaction was allowed to continue for an additional 2 hours at 70 ° C. followed by another 2 hours at 85 ° C. Heated and stirred (known as “heat treatment step”).

  Numerous levels of NaMPSA were evaluated. Its execution is listed in Table 2.1.

Table 2.1
i) Measurement in MeOH 1) 1 g NaPS in 25 g water used for heat treatment 2) Scale-up of Example 4 in a 4 liter reactor

TSC Test Method The percentage total solids (TSC) is determined by weighing a sample of material before and after 2 hours of drying under an IR lamp.

(W1 = Weight of sample container and W2 = Weight of container and sample before drying W3 = Weight of container and sample after drying)

  Kv was measured as described above using methanol as the solvent.

  Example 2.8 above was slightly different from the other examples above in that a “seed” containing VAc was created in the reactor at the start of the reaction. 200 g of water, NaMPSA (0.5 g) and VAc (5 g) were charged to a 1 liter reactor and heated to 70 ° C. with stirring. When the temperature reached 70 ° C., 4 g of NaPS aqueous solution (50 g) was introduced. After 5 minutes, the delayed addition of monomer (200 g VAc mixed with 50 g IPA) and an aqueous solution of NaPS (3 g) (50 g) were separately fed over 1 hour. When these additions were completed, 1 mL of hydrogen peroxide solution (35 wt%) was added to the reactor and the reaction was heated and stirred at 70 ° C. for an additional 2 hours and then immediately at 85 ° C. for an additional 2 hours (“ Known as "heat treatment process").

  The pH of Examples 2.1-2.8 was found to be somewhat lower, which can hydrolyze acetate groups to hydroxyl groups at elevated temperatures. Additional polymers according to the invention were synthesized in the presence of a buffer to form an emulsion with a higher pH (Table 2.2).

The general method used will now be described. 250 g of water and 3.5 g of NaMPSA were mixed in a 1 liter reactor and heated to 70 ° C. with stirring. When the temperature reached 70 ° C., 10 g of NaPS aqueous solution (7.4 wt%) was introduced. After 5 minutes, the delayed addition monomer (200 g VAc mixed with 50 g IPA) and 40 g NaPS aqueous solution (7.4 wt%) were individually fed into the reactor over 1 hour. At the same time (but on a different time scale), buffer was also added. Upon completion of monomer and NaPS addition, 1 mL of hydrogen peroxide (H ₂ O ₂ ) was added and the reaction was further heat treated at 70 ° C. for 2 hours and 85 ° C. for 2 hours.

Table 2.2
i) Measured in MeOH 1) No H ₂ O ₂ added 2) NaMPSA feed: 250 g H ₂ O, 1 g initial NaMPSA. As with the NaPS solution, 250 g of VAc, IPA of 75 g, NaPS 6 g of of _{H 2} O 50 g, and NaMPSA of 2.5g of of _{H 2} O 50 g, the SB of 4g of SB and 4g, Individually fed over 1 hour. When the feeding was completed, 1 mL of H ₂ O ₂ was added, and the reaction system was further reacted at 70 ° C. for 2 hours and at 85 ° C. for 2 hours.

  In Table 2.2, feeding over 30 minutes at t = 30 minutes means starting the addition of the buffer 30 minutes after the initial charge of monomer and initiator and the buffer for 30 minutes. Is defined as being added to Similarly, feeding for 1 hour at t = 0 is defined as the start of buffer addition at the same time as the initial charge of monomer and initiator and the addition of buffer to the reactor over 1 hour. Is done.

  It can be seen that the final emulsion pH is greater than 5 in the examples with buffer.

  A further example of a polymer emulsion for use according to the present invention was synthesized using NDM as a chain transfer agent.

Table 2.3

  Example 2.14A was based on Example 2.14, but NDM was used as the chain transfer agent. It has been found that reducing the amount of IPA destabilizes the resulting emulsion. Although it was found that replacing IPA with NDM formed a stable emulsion, the resulting polymer (apart from Example 2.14A) was insoluble in methanol.

The emulsions in the above examples were self-stabilized, that is, no surfactant or colloid was added to stabilize the emulsion. Additional emulsions were synthesized using various surfactants and colloids. The reaction was carried out at 70 ° C. using 250 g H ₂ O, 3.5 g NaMPSA, 1.5 g surfactant, 150 g VAc, 50 g IPA, 8 g NaPS in 50 g H ₂ O. As with the NaPS solution, the VAc and IPA solutions were fed over 1 hour. Thereafter, at the end of the addition, the reaction system was reacted at 70 ° C. for 2 hours and at 85 ° C. for 2 hours.

Table 2.4
1-based on Example 2.4 2-based on Example 2.12.

  The emulsion formed with SDBS was found to be stable, but the polymer prepared in the presence of SDS coagulated.

  The polymer emulsion for use according to the invention is a polyvinyl alcohol colloid, in this case Alcotex® 88-47 (provided by Synthomer, UK), ie having a degree of hydrolysis of 86.7-88.7 mol. % And the viscosity is 45-49 mPa.s. It was synthesized using poly (vinyl alcohol) (4% (w / w) aqueous solution, 20 ° C.) which is s. The colloid was introduced into the emulsion formulation by various methods: first addition, late addition and later addition. The results are shown in Table 2.5.

For Example 2.17, 250 g water, 5 g VAc, 2 g Alcotex®, and 0.5 g NaMPSA were mixed in a 1 liter reactor and heated to 70 ° C. When the temperature reached 70 ° C., 10 g of NaPS aqueous solution (7.4 wt%) was introduced. After 5 minutes, the monomer added late (200 g VAc mixed with 50 g IPA), 40 g NaPS aqueous solution at 7.4 wt%, and 4 g sodium bicarbonate and 4 g in 50 g H ₂ O A solution consisting of sodium citrate and 3 g NaMPSA was fed separately over 1 hour. When the addition was complete, 1 mL of H ₂ O ₂ was added and the reaction was further heat treated at 70 ° C. for 2 hours and 85 ° C. for 2 hours. The process for the other examples was as shown in Table 2.5.

c) condensed d) destabilized when stored at room temperature Table 2.5

  The emulsion of Example 2.17 exhibited a TSC of 35%, a conversion of 95%, a K value of 37, and a pH of 5.0. The examples and comparative examples in Table 2.5 suggest that for this particular polymer (especially when the reaction system is buffered) it is desirable to have some colloid in the initial reaction mixture. Is done.

An emulsion was formed without IPA and using polyvinyl alcohol colloid instead. The emulsion polymer of Example 2.20 was synthesized as follows. 300 g of distilled water and 10 g of M5-88 (Celvol® 205 polyvinyl alcohol provided by Celanese Corporation) were introduced into a 1 liter reactor and the temperature was set at 80 ° C. When this temperature was reached and the PVOH was completely solubilized, 200 g of VAc was added over a period of about 2 hours (at 1.79 mL / min). At the same time, the following solution was added over approximately 2 hours (at 0.4 mL / min); i) 1 g NaPS in 50 g distilled water, and ii) 1.2 g sodium bicarbonate in 50 g distilled water And 1.2 g sodium citrate and 2.5 g NaMPSA. Upon completion of the addition, the reaction system was further heat treated at 80 ° C. for 1 hour. The characteristics of the emulsion are:
GC: 1.5% VAc
K value: 74.3
TSC: 35.8%
pH: 4.7
Particle size: 440nm
Met.

  Residual vinyl acetate measurements were performed using a Perkin Elmer Turbomatrix® headspace sampling device. 0.5 g of sample was weighed into a headspace vial. 1 mL of water was added followed by 2 mL of internal standard (1,4-dioxane provided by Sigma Aldrich Co. LLC). The headspace vial was tightly stoppered and placed on a shaker for 30 minutes before mounting in the headspace carousel.

  Prior to injecting headspace vapor into the GC equipped with a flame ionization detector (FID), the vial was heated at 90 ° C. for 1 hour.

  As an example of an alternative colloid, cellulosic stabilizers were used. The formulation was based on Example 2.20 in the presence of hydroxypropyl methylcellulose F50® provided by The Dow Chemical Company at 80 ° C.

Table 2.5a

  Additional polymers used in accordance with the present invention were made by first synthesizing a polyvinyl acetate seed and then adding the remaining vinyl acetate, NaMPSA and sodium persulfate. Examples are shown in Table 2.6.

Table 2.6
SVS: sodium vinyl sulfonate AHPS: 3-allyloxy-2-hydroxy-1-propanesulfonic acid MA80: sodium dihexyl sulfosuccinate

  The examples in Table 2.6 demonstrate that in addition to NaMPSA, ion-containing monomers may be used.

  From this, the synthesis | combination of the emulsion polymer of Table 2.6 is demonstrated below.

Example 2.21
900 g of distilled water was introduced into the 4 liter reactor and the temperature was set at 80 ° C. When that temperature was reached, 2.2 g NaPS was introduced with stirring (150 rpm) and 60 g VAc was fed over about 30 minutes (at 2.14 mL / min). At the end of the addition, 540 g of VAc was added at 4.8 mL / min over about 2 hours, while at the same time two feeds of the next solution were added at 0.8 mL / min over about 2 hours; i A) 0.8 g NaPS in 100 g distilled water, and ii) 0.75 g sodium bicarbonate, 0.75 g sodium citrate and 10.5 g NaMPSA in 100 g distilled water. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour.

Example 2.22
Example 2.21 is repeated except that 0.75 g of sodium citrate and 0.75 g of sodium bicarbonate are charged into the batch.

Example 2.25
225 g of distilled water was introduced into the 1 liter reactor and the temperature was set at 80 ° C. When this temperature was reached, 0.55 g NaPS was introduced with stirring (150 rpm) and 15 g VAc was added over about 30 minutes (at 0.5 mL / min). At the end of the addition, 135 g of VAc was added over a period of about 2 hours (at 1.2 mL / min), while at the same time two feeds of the next solution were added over a period of about 2 hours (at 0.2 mL / min). Added: i) 0.2 g NaPS in 25 g distilled water, and ii) 0.2 g sodium bicarbonate, 0.2 g sodium citrate, 2.5 g NaMPSA and 1.5 g in 25 g distilled water. SVS. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour.

Example 2.29
225 g distilled water and 0.2 g sodium bicarbonate, 0.2 g sodium citrate were introduced into the 1 liter reactor and the temperature was set at 80 ° C. When that temperature was reached, 0.55 g NaPS was introduced with stirring (150 rpm) and 15 g VAc was added at 0.5 mL / min over about 30 minutes. At the end of the addition, 135 g of VAc was added at 1.2 mL / min over about 2 hours, while at the same time two feeds of the following solution were added at 0.2 mL / min over about 2 hours: i ) 0.2 g NaPS in 25 g distilled water, and ii) ii) 3.5 g NaMPSA and 1.65 g aerosol MA-80 (sodium dihexyl sulfosuccinate) in 25 g distilled water. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour.

Example 2.23
900 g distilled water, 1.3 g sodium bicarbonate and 1.3 g sodium citrate were introduced into the 4 liter reactor and the temperature was set to 80 ° C. When this temperature was reached, 2.2 g NaPS was introduced under stirring (150 rpm) and 60 g VAc was fed over about 30 minutes (at 2.14 mL / min). At the end of the addition, 690 g of VAc is added over approximately 2 hours and 40 minutes (at 4.6 mL / min); at the same time, the two feeds of the next solution are added over approximately 2 hours and 40 minutes (0.63 mL). Added): i) 1.1 g NaPS in 100 g distilled water, and ii) 13.1 g NaMPSA in 100 g distilled water. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour.

Example 2.30
225 g distilled water and 0.2 g sodium bicarbonate, 0.2 g sodium citrate were introduced into the 1 liter reactor and the temperature was set at 80 ° C. When that temperature was reached, 0.55 g NaPS was introduced with stirring (150 rpm) and 15 g VAc was added over about 30 minutes (at 0.5 mL / min). At the end of the addition, 135 g of VAc is added over a period of about 2 hours (at 1.2 mL / min); at the same time, the next solution, 0.2 g NaPS in 25 g distilled water, 1.65 g MA-80 is added. At 0.2 mL / min over about 2 hours. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour.

Example 2.26
Repeat Example 2.25 except that 0.2 g sodium bicarbonate and 0.2 g sodium citrate were charged into the batch and ii) was 3 g SVS (sodium vinyl sulfonate) in 25 g distilled water. It is.

Example 2.28
Example 2.22 is repeated except that solution ii) is 6.5 g of 3-allyloxy-2-hydroxy-1-propanesulfonic acid (AHPS) at 40 wt% in 21 g of distilled water.

Example 2.27
Example 2.28 is repeated except that solution ii) is 5.25 g 2-acrylamino-2-methylpropanesulfonic acid sodium salt (AMPS) at 50 wt% in 22.4 g distilled water.

  Further experiments were performed by incorporating sulfur-containing monomers into the “seed”. Polyvinyl alcohol was used to stabilize the emulsion formed.

  Further examples of polymers for use according to the present invention were synthesized with higher levels of chain transfer agent, persulfate, or the addition of a secondary initiator (hydrogen peroxide).

Table 2.7

  The synthesis was based on Example 2.22. It has been demonstrated that increasing the amount of chain transfer agent leads to low K values.

  A further example of a polymer for use according to the present invention is shown using the crosslinking monomer TTT (1,3,5-triallyl-1,3,5-triazine-2,4,6-trione). Synthesized based on the synthesis for 2.22. Example 2.36 contained 1% w / w TTT relative to vinyl acetate and Example 2.37 contained 5% w / w TT relative to vinyl acetate, both of which were methanol and THF. Insoluble polymer was produced.

  Polymer examples for use according to the present invention were synthesized using one or more monomers other than VAc. The results are shown in Table 2.8 below.

Table 2.8

In the table, MMA is methyl methacrylate and BA is butyl acrylate. All runs were performed at 80 ° C. using 275 g H ₂ O, 0.2 g SB, 0.75 g SC, 0.75 g NaPS, 150 g (mixed) acrylate monomer (s), 2.6 g NaMPSA. Made in

These polymers were found to be insoluble in methanol, so molecular weight data (M _w and M _n ) were obtained by size exclusion chromatography (SEC) in THF solution (gel permeation chromatography, also known as GPC). It was measured. Samples were PL-GPC-50 (registered) by an automated sampler using stabilized THF as the mobile phase and three consecutive PL gel® columns each having dimensions of 300 mm × 7.5 mm × 10 μm. Was injected into the trademark system. The system was calibrated using polystyrene standards, PS High Eastals provided by Agilent Technologies with an Mp molecular weight range of 6,035,000-580 g / mol. In this case, M _n = number average molecular weight, M _w = weight average molecular weight, and polydispersity (PDI) are defined as M _w / M _n .

  Further examples of polymers for use in accordance with the present invention were synthesized with various ratios of sulfonated monomers in the seed, with various sulfonated monomer contents and various solids.

1) Adjust pH with 20% aqueous sodium bicarbonate solution 2) Use 1% NDM% (w / w _VAc ) 3) Add sulfonated monomer as described below 4) As described below Add delayed initiator solution Table 2.9

Example 2.42
225 g distilled water, 2 g sodium bicarbonate, 2 g sodium citrate, and 1 g NaMPSA were introduced into the 1 liter reactor and the temperature was set at 80 ° C. When that temperature was reached, 1 g of NaPS was introduced with stirring (150 rpm) and 15 g of VAc was added over about 30 minutes (at 0.5 mL / min). At the end of the addition, 135 g of VAc is added over approximately 2 hours (at 1.2 mL / min); at the same time the next solution i) 0.5 g NaPS in 25 g distilled water, and ii) 25 g 2 g NaMPSA in distilled water was added at 0.2 mL / min over about 2 hours. When the addition was complete, the reaction was further heat treated at 85 ° C. for 2 hours.

Example 2.57
800 g distilled water, 10 g sodium bicarbonate, 10 g sodium citrate were introduced into the 4 liter reactor and the temperature was set at 80 ° C. When that temperature was reached, 6.72 g of NaPS was introduced under stirring (150 rpm) and 48 g of VAc was added along with 0.48 g of NDM over about 1 hour (0.86 mL / min). At the end of the addition, 912 g of VAc is added with 9.12 g of NDM over about 4 hours and 11 minutes (at 3.89 mL / min); at the same time the next solution, i) 2.88 g in 100 g of distilled water. Of NaPS, and ii) 38.4 g AMPS in 62 g distilled water was added at 0.4 mL / min over about 2 hours. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour.

Example 2.58
800 g distilled water, 10 g sodium bicarbonate, 10 g sodium citrate were introduced into the 4 liter reactor and the temperature was set at 80 ° C. When that temperature is reached, 6.72 g NaPS is introduced under stirring (150 rpm) and an aqueous solution of 38.4 g AMPS in 62 g distilled water is added at 0.3 mL / min over about 5 hours and 11 minutes. did. At the same time, 48 g of VAc was added along with 0.48 g of NDM over about 1 hour (0.86 mL / min). At the end of the VAc-NDM addition, 912 g of VAc was added along with 9.12 g of NDM over about 4 hours and 11 minutes (3.9 mL / min) and 2.88 g of NaPS in 100 g of distilled water was added for about 2 hours. Over a period of 0.4 mL / min. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour.

Example 2.59
187 g of distilled water, 1.25 g of sodium bicarbonate, 1.25 g of sodium citrate were introduced into the 1 liter reactor and the temperature was set at 80 ° C. When that temperature is reached, 1.58 g NaPS solubilized in 12.5 g distilled water, and 48 g VAc are added over a period of about 1 hour with stirring (150 rpm) with 0.48 g NDM. did. After 1 hour, at the end of the addition, 228 g of VAc was added over a period of about 4 hours and 11 minutes with 2.28 g of NDM; at the same time, i) 0.72 g of NaPS in 25 g of distilled water, ii) 9.6 g AMPS in 15.4 g distilled water was added over about 4 hours and 11 minutes. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour.

  Various formulations were scaled up in 500 liter (0.5 T) and 1000 liter (1.0 T) reactors.

Table 2.10

Example 2.60
277.7 kg of distilled water, 0.292 kg of sodium bicarbonate and 0.292 kg of sodium citrate were introduced into the reactor and the temperature was set at 80 ° C. When that temperature was reached, 0.641 kg of NaPS solubilized in 6.408 kg of distilled water was introduced under stirring. 17.494 kg of VAc was added over about 30 minutes. At the end of the addition, 157.445 kg of VAc was added over about 2 hours, while at the same time the following solution: i) 0.233 kg NaPS in 21.696 kg distilled water, ii) 14.916 kg distilled water 7.013 kg of AMPS was added over about 2 hours. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour. At 65 ° C., 0.053 kg of tBHP was charged, and after 10 minutes, 0.053 kg of ascorbic acid solubilized in 0.534 kg of distilled water was added over 10 minutes.

Example 2.61
271.59 kg of distilled water, 2.355 kg of sodium bicarbonate, 2.355 kg of sodium citrate and 4.716 kg of AMPS were introduced into the reactor and the temperature was set to 80 ° C. When that temperature was reached, 1.177 kg of NaPS solubilized in 11.773 kg of distilled water was introduced under stirring. 17.659 kg of VAc was added over about 30 minutes. At the end of the addition, 158.929 kg of VAc was added over about 2 hours, while at the same time the following solution: i) 0.589 kg NaPS in 16.688 kg distilled water, ii) in 14.916 kg distilled water 2.359 kg of AMPS was added over about 2 hours. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour. At 65 ° C., 0.053 kg of tBHP was charged, and after 10 minutes, 0.053 kg of ascorbic acid solubilized in 0.534 kg of distilled water was added over 10 minutes.

Example 2.62.
Example 2.61 was repeated by scaling up with a 1T reactor instead of a 0.5T reactor.

Example 2.63
520 kg of distilled water, 4.16 kg of sodium bicarbonate, 4.16 kg of sodium citrate were introduced into the reactor and the temperature was set at 80 ° C. When that temperature was reached, 2.8 kg NaPS solubilized in 3 kg distilled water was introduced under stirring. 20 kg of VAc mixed with 0.2 kg of NDM was added over about 1 hour. At the end of the addition, 380 kg of VAc mixed with 3.8 kg of NDM was added over a period of about 4 hours, while at the same time i) 1.2 kg NaPS in 27.6 kg distilled water, ii) 16 kg AMPS in 12.8 kg distilled water was added over about 4 hours. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour. At 65 ° C., 0.15 kg tBHP was charged and after 10 minutes 0.2 kg ascorbic acid solubilized in 2.8 kg distilled water was added over 10 minutes. At 30 ° C., 0.1 kg antifoam and 0.686 kg H ₂ O ₂ were added.

Example 2.64
215.1 kg of distilled water, 2.486 kg of sodium bicarbonate, 2.48 kg of sodium citrate were introduced into the reactor and the temperature was set at 80 ° C. When that temperature was reached, 1.673 kg NaPS was introduced under stirring. 11.95 kg of VAc mixed with 0.12 kg of NDM was added over about 1 hour. At the end of the addition, 227.05 kg of VAc mixed with 2.271 kg of NDM was added over about 4 hours, while at the same time the following solution: i) 0.717 kg of NaPS in 16.491 kg of distilled water, ii) 9.56 kg AMPS in 7.648 kg distilled water was added over about 4 hours. When the addition was complete, the reaction was further heated at 80 ° C. for 1 hour. At 65 ° C., 0.089 kg of tBHP was charged, and 10 minutes later, 0.086 kg of ascorbic acid solubilized in 0.621 kg of distilled water was added over 10 minutes.

Example 2.65
Example 2.63 was scaled up with a 1T reactor instead of a 0.5T reactor, except that 0.1 kg of antifoam and 0.403 kg of H ₂ O ₂ were added at 30 ° C. at the end of the run. And repeated.

Example 2.66
390 kg of distilled water, 5.4 kg of sodium bicarbonate, 5.4 kg of sodium citrate were introduced into the reactor and the temperature was set at 80 ° C. When that temperature was reached, 3.64 kg of NaPS was introduced under stirring. 26 kg of VAc mixed with 0.26 kg of NDM was added over about 1 hour. At the end of the addition, 494 kg of VAc mixed with 4.94 kg of NDM is added over about 4 hours, while 20.8 kg of AMPS in 14.56 kg of distilled water is added over about 4 hours, 1.56 kg NaPS in 33.8 kg distilled water was added over about 4 hours and 15 minutes. When the addition of NaPS solution was complete, the reaction was further heated at 85 ° C. for 1 hour. At 75 ° C. and 65 ° C., 0.193 kg of tBHP was charged, and after 10 minutes, 0.169 kg of ascorbic acid solubilized in 1.352 kg of distilled water was fed over 10 minutes. At 30 ° C., 0.13 kg of antifoam and 0.446 kg of H ₂ O ₂ were added.

Example 2.67
390 kg of distilled water, 5.4 kg of sodium bicarbonate, 5.4 kg of sodium citrate were introduced into the reactor and the temperature was set at 80 ° C. When that temperature was reached, 3.64 kg of NaPS was introduced under stirring. 26 kg of VAc mixed with 0.31 kg of NDM was added over about 1 hour. At the end of the addition, 494 kg of VAc mixed with 5.928 kg of NDM is added over about 4 hours, while at the same time 20.8 kg of AMPS in 14.56 kg of distilled water is added over about 4 hours, 1.56 kg NaPS in 33.8 kg distilled water was added over about 4 hours and 15 minutes. When the addition of NaPS solution was complete, the reaction was further heated at 85 ° C. for 1 hour. At 75 ° C., 0.193 kg of tBHP was charged, and 10 minutes later, 0.156 kg of ascorbic acid solubilized in 1.352 kg of distilled water was supplied over 10 minutes. At 30 ° C., 0.13 kg of antifoam and 0.446 kg of H ₂ O ₂ were added.

  In general, emulsions obtained using a seed stage process were thawed after a freeze-thaw cycle (emulsion sample (2 mL) was frozen for 2 hours. This cycle was repeated three times and stability was assessed visually). )).

  Moreover, these emulsions were measured by shear stability (pumping the emulsions at 10, 20, 30 and 40 mL / min for 1 hour in tubes (diameter = 0.8 mm) at 30%, 20% and 10% TSC. Viscosity was measured before and after these experiments using a Brookfield DV-I viscometer (registered trademark), measured using spindle 1 at 25 ° C., with stability defined as a measurement that remains within ± 2 mPas. Was also demonstrated.

2. B. Manufacture of PVC using a non-hydrolyzed copolymer obtained by emulsion polymerization As will be explained, the above polymer was used as a secondary precipitation inhibitor in the emulsion polymerization of vinyl chloride.

The reaction was carried out in a 1 liter Buchi® stainless steel reactor with a PVC pilot plant using the following conditions.
Temperature: 57 ° C
Stirrer speed: 750 rpm
Stirrer type: Standard (as provided)
Table 2.11.

  Demineralized water, suspending agent, buffer and initiator are all 1 liter Buchi® stainless steel reaction (pre-coated with Alcotex® 225 accumulation inhibitor provided by Synthomer, UK) The container was filled and assembled on the tool. Strategies were planned to give the final particle size unchanged from typical commercial products. The reactor was then pressure tested and degassed to atmosphere, after which the vinyl chloride monomer was charged with a volume atomizer under nitrogen pressure. A suspension of vinyl chloride was prepared by stirring at about 750 rpm. The reactor was then heated to the desired polymerization temperature of 57 ° C. within 6 minutes and maintained at 750 rpm until the maximum pressure was recorded, and the reaction was allowed to proceed (cooling and atmospheric pressure) after a pressure drop of 0.2 MPa. Stopped by degassing). The reactor was then evacuated to about 50 kPa for 45 minutes. The reactor contents were then gently transferred to a filter funnel and washed twice with 1% (w / w) sodium lauryl sulfate solution (as an antistatic treatment). Thereafter, the sample was placed in a convection fan oven at 50 ° C. for 12 hours and dried.

The resulting PVC samples were analyzed for particle size (D ₅₀ ), particle size distribution (GSD), low temperature plasticizer absorbency (CPA), bulk density (BD) and fill factor (PF). The measurement of these parameters is discussed above in Part 1.

Table 2.12
* No secondary precipitation inhibitor ** Average result
¹ , C.I. Ex. 401 is solid polyvinyl acetate M30 (registered trademark) provided by Synthomer (UK), Mw = 85,000 g / mol.
² , C.I. Ex. 402 is an acrylic copolymer dispersion Plextol® R760 supplied by Synthomer (Germany).

  The example numbers in Table 2.12 indicate what the polymer used as the secondary suspending agent is (if the polymer is according to the invention). The polymer was C.I. with 500 ppm polymer + stabilizer based on vinyl chloride. Ex. Except for 402, it was filled at a level of 500 ppm based on vinyl chloride.

  The data in Table 2.12 clearly show that the example emulsion polymers can be successfully used as secondary suspending agents, especially for suspension polymerization of vinyl chloride. The CPA values of the polymers produced using the polymers of the examples are C.I., a conventional secondary precipitation inhibitor. Ex. This is comparable to the CPA value exhibited by polymers synthesized using 2, and in many cases is superior. The CPA value appears to vary with the amount of sulfur-containing monomer in the secondary suspending agent, and is optimal at a sulfur-containing monomer content of about 2-3% (w / w). Furthermore, the particle size distribution (GSD) of PVC made using the example polymers is typically lower than that of PVC made using conventional secondary suspending agents.

  Samples obtained using the seed stage process were also tested with sPVC (suspension polymerization of vinyl chloride monomer); in addition, a smaller amount of secondary suspending agent in the formulation was evaluated.

Table 2.13
^* No secondary precipitation inhibitor
^** Average result (1)-Emulsions stabilized in MeOH

  The results in Table 2.13 indicate that polymer emulsions produced in the presence of seeds performed well with low loadings.

  In general, good particle size control was observed. Polymers produced on a large scale (1T) performed similarly to those produced on a laboratory scale.

  PVC was produced in a 10 liter reactor using the polymer of the present invention. The experimental results are shown in Table 2.14.

* Table 2.14 in the presence of significant amounts of oxygen

  From the data obtained in the 10 liter PVC pilot plant, the particle size value obtained for the sulfonated PVAc secondary precipitation inhibitor is in the range of 130-180 μm, and the CPA value is a conventional secondary precipitation inhibitor. C. Ex. Although close to 2 to 28-28%, it has been shown that there is the advantage of better atomic efficiency in their preparation and in the absence of solvent.

  While the invention has been described and illustrated with reference to specific embodiments, those skilled in the art will appreciate that the invention is suitable for many different variations not specifically exemplified herein. I will. Thus, specific possible modifications will be described by way of example only.

  The above examples illustrate the use of the polymer as a secondary suspending agent to produce PVC. The polymer may be used to produce other polymers.

  The polymer used as the secondary precipitation inhibitor may have a composition different from that described in the above examples.

  VCM desorption kinetics were performed on PVC resin obtained in a 10 liter reactor using sulfonated PVAc and C.I. Ex. Compared to 301.

  After the reaction, the resin was filtered and dried in an oven at 70 ° C. Samples were taken at 0, 5, 15, 30, 60 and 120 minutes. For the first three samples at 0, 5, and 15 minutes, 0.1 g PVC sample was dissolved in 10 mL cyclohexanone, whereas for samples at 30, 60, and 120 minutes, 0.25 g PVC was 10 mL. Dissolved in cyclohexanone. After the addition of cyclohexane, the sample was left stirring until the PVC was dissolved.

  The level of residual VCM in each sample was measured by the GC headspace method with a detection limit of 1 ppm and a quantification limit of 50 ppm. 0.1 / 0.25 g PVC sample was dissolved in 10 ml cyclohexanone in a 20 mL headspace vial. VCM was extracted from the vial headspace using PDMS carboxen SPME fiber (provided by Supelco) at 50 ° C. for 30 minutes. The SPME fiber was then desorbed for 3 minutes in a Shimadzu GC-MS® injector and flowed using a 60M MP-5 (1.25 mm + 1 μm) ® column (provided by Agilent Technologies). A series of DCM standards in the range of 100-0.1 ppm were prepared and injected directly into the Shimadzu GC-MS® and run similarly.

  The results of VCM (%) desorption experiments on PVC resins produced using various polymers as secondary precipitation inhibitors are shown in FIG. 1 as a function of time (C. Ex. 2 (white triangle-1 liter reaction). Reactor, black triangle-10 liter reactor), Example 2.61 (black diamond-500 ppm, 10 liter reactor), Example 2.64 (black square-400 ppm, 10 liter reactor, white square-300 ppm, 10 Liter reactor) and Example 2.63 (black circle—400 ppm, 10 liter reactor, white circle—300 ppm, 10 liter reactor)).

  As shown in FIG. 1, all samples showed similar behavior during the first 20 minutes of desorption. At 30 minutes and thereafter, PVC resins made in the presence of sulfonated PVAc gave lower VCM% values than those made using standard secondary agents. It should be noted that the latter PVC had the highest CPA (30.2%) in Table 2.14. In addition, FIG. 1 indicates that VCM desorption was more efficient for PVC resins made with 400 ppm or 300 ppm of the sulfonated polymer of the present invention.

  The PVC polymerization examples demonstrated in the present invention are of the type known as cold charge, where the primary and secondary suspending agents are present at the beginning of a series of charges. Other methods are known. Generally, water, protective colloid (s) and further optional additives are initially charged to the reactor, followed by addition of liquefied vinyl chloride monomer and optional comonomer (s). Optionally, the protective colloid may be loaded into the preheat reactor with some or all of the aqueous phase simultaneously with the vinyl chloride monomer. Optionally, simultaneously with some or all of the hot demineralized water that forms an aqueous phase so that the reactor is at or near the desired polymerization temperature by the time of filling with water, colloid (s) and monomer (eg vinyl chloride). , May be filled with a protective colloid. This process is known as “hot charging”. Optionally, the initiator is then charged to the reactor.

  The polyvinyl alcohol secondary precipitation inhibitor may be used together with other protective colloids (for example, with primary protective colloids and other secondary and tertiary protective colloids). Specific examples of protective colloids are listed in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, 1992, pages 722, Table 3.

  While the invention has been described and illustrated with reference to specific embodiments, those skilled in the art will appreciate that the invention is suitable for many different variations not specifically exemplified herein. I will. Thus, specific possible modifications will be described by way of example only.

  The above examples illustrate the use of the polymer as a secondary suspending agent to produce PVC. The polymer may be used to produce other polymers.

  The polymer used as the secondary precipitation inhibitor may have a composition different from that described in the above examples.

  Where the foregoing description refers to completeness or elements with known, obvious or predictable equivalents, such equivalents are hereby incorporated as if individually set forth. The true scope of the invention should be determined with reference to the claims, and should be construed to include such equivalents. It is also understood by the reader that the completeness or features of the present invention described as preferred, beneficial, convenient, etc. are optional and do not limit the scope of the independent claims. Will be done. Furthermore, while any such completeness or feature may be beneficial in some embodiments of the invention, it may not be desirable in other embodiments and therefore may not be present. Should be understood.

Claims (34)

Use of a polymer as a secondary suspending agent in a suspension polymerization reaction, the polymer comprising:
(I) a residue of at least one ester-containing monomer, wherein the ester-containing monomer (s) comprise one polymerizable carbon-carbon double bond and ester group per monomer, and (ii) sulfonate, sulfonic acid, sulfone The monomer (s) containing acid ester, sulfonamide, or sulfonyl halide groups contain one polymerizable carbon-carbon double bond and sulfonate, sulfonic acid, sulfonate ester, sulfonamide, or sulfonyl halide group per monomer One or more residues of at least one monomer comprising a sulfonate, sulfonic acid, sulfonate ester, sulfonamide, or sulfonyl halide group,
Use of the polymer, wherein the polymer is optionally partially hydrolyzed so that part of the ester group forms an alcoholic group, the degree of hydrolysis of the polymer being 0-30 mol%.
Use according to claim 1, comprising the use of an emulsion of a polymer.
Use according to claim 1, wherein the polymer solution is added to a suspension polymerization reaction mixture.
Use according to any of the preceding claims, wherein the polymer is made by emulsion polymerization or derived from the emulsion polymer.
Use according to claim 4, wherein the polymer is formed by emulsion polymerization in the presence of seeds.
6. Use according to claim 5, wherein the species comprises a seed polymer.
Use according to any of claims 1 to 3, wherein the polymer is made by dispersion or bulk polymerization or bulk polymerization in solution.
Use according to any of the preceding claims, wherein the polymer comprises a residue of one or more ester-containing monomers.
Use according to any of the preceding claims, wherein the ester-containing monomer comprises a polymerizable C = C group bonded to an ester group, and there is no linking group between the polymerizable C = C group and the ester group. .
10. Use according to claim 9, wherein the ester group is arranged in the -O- moiety adjacent to the C = C group.
Use according to claim 9, wherein the ester group has a C = O moiety adjacent to the C = C group.
Use according to any of the preceding claims, wherein C = C of the ester-containing monomer is substituted at 1, 2 or 3 positions.
The ester-containing monomers are vinyl acetate, vinyl benzoate, vinyl 4-t-butylbenzoate, vinyl chloroformate, vinyl cinnamate, vinyl decanoate, vinyl neononanoate, vinyl neodecanoate, vinyl pivalate, vinyl propio. Nate, vinyl stearate, vinyl trifluoroacetate, vinyl valerate, methyl vinyl acetate, propenyl acetate, methyl propenyl acetate, ethyl propenyl acetate, butenyl acetate, methyl butenyl acetate, vinyl propanoate, propenyl propanoate, vinyl Butyrate, vinyl hexanoate, vinyl heptanoate, vinyl octanoate, vinyl 2-propylheptanoate, vinyl nonanoate, vinyl neonona Benzoate or vinyl trifluoroacetate containing, Use according to any one of the preceding claims,.
Use according to any of the preceding claims, wherein the polymer comprises a residue of one or more monomers comprising sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide groups.
The monomer containing a sulfonate, sulfonic acid, sulfonate ester, sulfonamido, or sulfonyl halide group is between the polymerizable C = C group and the sulfonate, sulfonic acid, sulfonate ester, sulfonamido, or sulfonyl halide group. The use according to any of the preceding claims comprising a combination of
The monomer (s) containing a sulfonate, sulfonic acid, sulfonate ester, sulfonamide, or sulfonyl halide group are sodium vinyl sulfonate, sodium allyl sulfonate, 2-methyl-2-propene-1-sulfonic acid sodium salt and 2-acrylamido-2-methylpropanesulfonic acid sodium salt, 3-sulfopropyl (meth) acrylate, 1-allyloxy-2-hydroxypropyl sodium sulfonate, acrylic acid or methacrylic acid linear or branched C ₁ -C ₁₀ Use according to any of the preceding claims, comprising an alkylsulfonamide or an ω-alkene-1-sulfonic acid having 2 to 10 carbon atoms.
Use according to any of the preceding claims, wherein the copolymer comprises up to 5 mol% of monomer residues containing sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide groups.
Use according to any of the preceding claims, wherein the copolymer contains up to 3 mol% of monomer residues containing sulfonate, sulfonic acid, sulfonate ester, sulfonamide or sulfonyl halide groups.
6. The copolymer according to claim 1, wherein the copolymer contains 0.1 to 1.5 mol% of a monomer residue containing a sulfonate, sulfonic acid, sulfonic acid ester, sulfonamide, or sulfonyl halide group. use.
The copolymer comprises at least 90 residues of the at least one ester-containing monomer and at least 90 residues of the at least one monomer comprising a sulfonate, sulfonic acid, sulfonate ester, sulfonamide, or sulfonyl halide group. Optionally, a portion of the ester residue is hydrolyzed to provide a degree of hydrolysis of up to 60 mol%, the remainder of the polymer being the residue of the at least one ester-containing monomer, and sulfone. -Use according to any of the preceding claims, wherein the residue is not the residue of the at least one monomer comprising a sulfonic acid, sulfonic acid ester, sulfonamide or sulfonyl halide group.
Use according to any of the preceding claims, wherein the copolymer has not been hydrolyzed to a significant degree and the degree of hydrolysis is 10 mol% or less.
The use according to claim 21, wherein the degree of hydrolysis is substantially zero.
Use according to any of claims 1 to 20, wherein the degree of hydrolysis is 0 to 30 mol%.
A secondary suspending agent composition for suspension polymerization of vinyl compounds, comprising a solution or emulsion of a copolymer,
(I) a residue of at least one ester-containing monomer, wherein the ester-containing monomer (s) comprises one polymerizable carbon-carbon double bond and ester group per monomer, and (ii) sulfonate The monomer (s) containing sulfonic acid, sulfonic acid ester, sulfonamide, or sulfonyl halide group is one polymerizable carbon-carbon double bond and sulfonate per monomer, sulfonic acid, sulfonic acid ester, One or more residues of at least one monomer comprising a sulfonate, sulfonic acid, sulfonate ester, sulfonamide, or sulfonyl halide group comprising a sulfonamide or sulfonyl chloride group;
The polymer is optionally partially hydrolyzed so that a part of the ester group forms an alcoholic group, and the degree of hydrolysis of the polymer is 0 to 60 mol%. Secondary precipitation inhibitor composition for suspension polymerization of compounds.
A suspension polymerization reaction composition comprising:
It is a continuous phase polymerized with droplets in which one or more monomers are dispersed, wherein the one or more primary suspending agents, wherein at least one secondary suspending agent comprises a copolymer, (I) the residue of at least one ester-containing monomer, wherein the ester-containing monomer (s) contains one polymerizable carbon-carbon double bond per monomer and per ester group (Ii) one or more residues of at least one monomer comprising a sulfonate, sulfonate group, sulfonate ester group, sulfonamide group or sulfonyl halide group, the monomer (s) being a sulfonate , Sulfonic acid group, sulfonic acid ester group, sulfonamide group or sulfonyl halide group, the monomer (s) is per monomer and sulfonate, sulfonic acid group, sulfonic acid ester , Each containing a polymerizable carbon-carbon double bond per sulfonamide group or sulfonyl halide group, and the polymer is optionally partially hydrolyzed from the alcohol group to a portion of the ester group; A suspension polymerization reaction composition comprising a polymer having a degree of hydrolysis of 0 to 30 mol%.
26. The reaction composition of claim 25, wherein the one or more monomers to be polymerized comprise a monomer comprising a polymerizable vinyl (C = C) group and one or more comonomers.
27. The reaction composition of claim 25 or claim 26, wherein the primary suspending agent comprises one or more polyvinyl acetate having a degree of hydrolysis of about 70-90 mol%.
28. The reaction composition of claim 27, wherein the primary suspending agent comprises one or more cellulose polymers.
28. A reaction composition according to any of claims 24-27, wherein the reaction composition is suitable for radical addition polymerization.
100 parts by weight of the one or more monomers to be polymerized, 85 to 130 parts by weight of the continuous phase, 0.04 to 0.22 parts by weight of the primary precipitation inhibitor, and the secondary precipitation inhibitor 0 containing the polymer. The reaction composition according to any one of claims 25 to 28, comprising 0.001 to 0.20 parts by weight and 0.03 to 0.15 parts by weight of an initiator.
26. The weight of the primary suspending agent used in the composition is at least 0.5 times and optionally at least 5.0 times the weight of the secondary suspending agent comprising the polymer. 30-Reaction composition in any one of -29.
31. A reaction composition according to any of claims 25 to 30, wherein the composition comprises 100 to 800 ppm of the secondary suspending agent, based on the weight of the one or more monomers to be polymerized.
A method of producing a polymer using suspension polymerization, the method comprising:
(I) a residue of at least one ester-containing monomer, wherein the ester-containing monomer (s) comprises one polymerizable carbon-carbon double bond and ester group per monomer, and (ii) sulfonate The monomer (s) containing sulfonic acid, sulfonic acid ester, sulfonamide, or sulfonyl halide group is one polymerizable carbon-carbon double bond and sulfonate per monomer, sulfonic acid, sulfonic acid ester, One or more residues of sulfonate, sulfonic acid, sulfonate ester, sulfonamide, or sulfonyl halide group containing a sulfonamide or sulfonyl halide group,
The polymer is optionally partially hydrolyzed so that a portion of the ester group forms an alcoholic group,
A method for producing a polymer using suspension polymerization, comprising polymerizing one or more monomers in the presence of a secondary suspending agent having a hydrolysis degree of 0 to 30 mol% or less.
34. The method of claim 33, comprising forming a reaction composition according to any of claims 25-32.